Study on the Influence of Water Immersion on the Heating and Oxidation Stage of Bituminous Coal and the Evolution Law of Key Groups.

After a coal seam is mined, the coal remaining in the goaf is prone to flooding and spontaneous combustion accidents. To explore the reignition (secondary oxidation) characteristics of long-flame coal after oxidation and water immersion, the experimental methods of thermogravimetric analysis and infrared spectroscopy were used to analyze coal samples of oxidation first and then water immersion (FO) and samples of water immersion first and then oxidization (FI) at different pre-oxidation temperatures. The results showed that the content of main oxygen-containing functional groups (hydroxyl, carbonyl, and carboxyl groups) of the FO120 (oxidation 120 °C first and then water immersion) coal sample increased, and the FI 90 (water immersion first and then oxidization 90 °C) coal sample decreased. Pre-oxidation at 120 °C will slow down the decrease in the extent of low-temperature secondary oxidation TG, as the pre-oxidation temperature increases, the total heat release of the FO coal samples first increase and then decrease, and the heat released is high at 120 °C. The FI coal samples transfer active sites during the water immersion process, and the high pre-oxidation temperature leads to the rapid increase of the speed of the primary active site, which leads to the transformation between the secondary active site and the oxygen-containing group, resulting in the cleavage of the oxygen-containing group and increasing the heat production. Water immersion pre-oxidation performed under different conditions has the dual effects of promoting and inhibiting spontaneous coal combustion. This result provides a theoretical basis for preventing spontaneous combustion in coal-mined areas in shallow coal seams after soaking in water.

In order to reveal the reaction mechanism responsible for the spontaneous combustion of water-immersed coal, this study researched the changes in the physical and chemical structures of coal samples before and after water immersion. The results of the specific surface and pore size analyzer test showed that compared with the original coal sample, the microporous (<10 nm) ratio decreased, but the proportion of macropores (>50 nm) increased obviously in the water-immersed coal sample. Also, as the water immersion time increased, the proportion of micropores decreased from 78.5% to 74.2%, while the proportion of macropores increased from 8.5% to 13.4%. The increase in the number of macropores increased the exposure of coal to oxygen. The scanning electron microscopy (SEM) results showed that the surface pore diameter of the water-immersed coal sample increased obviously, the surface of the coal sample was rougher, and the adsorption and diffusion of oxygen were enhanced. The Fourier transform infrared (FTIR) experiment showed that the contents of hydroxyl and aliphatic groups with higher activity in water-immersed coal samples increased significantly. The content of hydroxyl groups increased in lignite, bituminite, and anthracite by 2.7%, 2.27%, and 0.11% respectively, while the contents of aromatic hydrocarbons and oxygen-containing functional groups showed relative decreases. Compared with the original coal, the physical and chemical structure of water-immersed coal changed obviously. Therefore, it was easier for the water-immersed coal to react with oxygen, and it was also prone to spontaneously ignite.

Liquid carbon dioxide has an excellent ability of endothermic cooling and inhibition on coal fire, which was an effective coal spontaneous combustion prevention technology. To analyze the oxidation characteristics and variation of apparent activation energies, a carboniferous–permian coal sample was investigated in O2/N2 and O2/CO2 atmospheres by the coal spontaneous combustion oxidation and the Fourier transform infrared spectroscopy experiments. The results indicated that with temperature, carbon monoxide (CO) concentration and oxygen (O2) consumption rate increased. While O2 concentration decreased, CO concentration and oxygen consumption rate reduced. At the same O2 concentration, the oxygen consumption rate and CO concentration on the O2/CO2 atmospheres were less than on the O2/N2 atmospheres. Therefore, O2 concentration reduced, or added CO2 significantly inhibited coal oxidation. As the temperature elevated, the apparent activation energy gradually increased. Furthermore, the apparent activation energy increased when the oxygen concentration reduced in the physical–chemical adsorption stage and the slow oxidation stage. In the rapid oxidation stage, the apparent activation energy lessened with increase in oxygen concentration. Through correlation analysis, the key functional groups in the physical–chemical adsorption stage were hydroxyl, C–O, –COO–, and aliphatic hydrocarbons. During the slow oxidation, the key functional groups were –COO– and aliphatic hydrocarbons. The key functional groups in the rapid oxidation stage were hydroxyl and C–O.

As a key parameter, the particle size of residual coal contributes greatly to its oxidation characteristics, so it is a significant and far-reaching topic to explore the role of different particle sizes in coal spontaneous combustion disaster. In this work, temperature-programmed system (TPS) was applied to analyze the oxygen consumption rate and CO and C2H4 production rules of six groups of coal samples with different particle sizes in the process of oxidation heating. The critical temperature (CT) and xerochasy temperature (XT) of different coal samples were obtained, and the coal oxidation process was divided into three stages (S1, slow oxidation stage; S2, fast oxidation stage; and S3, combustion stage). Then, the apparent activation energy (E) and pre-exponential factor (A) in three stages were regressed combined with Arrhenius formula. The results show that the smaller the coal particle size is, the larger the specific surface area is, the stronger the adsorption capacity of coal molecules and oxygen molecules is, resulting in the larger oxygen consumption rate. The values of CT and XT with particle size of 0.125-0.18mm and 2-4mm are the smallest and largest. For coal samples with the same particle size, the maximum values of E and A occur in stage S3 and the minimum values appear in stage S1. This is mainly due to the higher temperature of stage S3, which allows the activation of functional groups with higher apparent activation energy, stronger collisions between activated molecules, and more intense oxidation reactions.

Coal spontaneous combustion (CSC) not only leads to significant resource waste but also releases toxic and harmful gases such as CO, posing severe threats to the environment and human health. In actual mine production, complex mining conditions facilitate CO accumulation, while ventilation volume affects CO generation in working faces. This study investigated the influence of ventilation volume on CO generation patterns during coal low-temperature oxidation (LTO) through programmed temperature-rise experiments. Based on generation kinetics, the apparent activation energy characteristics of three LTO (slow oxidation stage, accelerated oxidation stage, violent oxidation stage) were clarified. Using in situ Fourier transform infrared spectroscopy (FTIR), variations in five major active groups during these three stages under different ventilation volumes were analyzed, revealing the dynamic distribution features of key active groups in coal samples. Finally, the structure-activity relationship between CO generation and critical active groups was established via principal component analysis (PCA). The findings indicate that the concentration, yield, and generation rate of CO gas during LTO of coal are positively correlated with ventilation volume. C = O and -OH are the key reactive functional groups governing CO generation, jointly dominating its production. Meanwhile, -COOH, C = C, -CH3, and -CH2- indirectly regulate the CO release process by modulating reaction pathways and activation energy changes. These discoveries reveal the structure-activity relationship between CO generation and key reactive functional groups during coal LTO, providing a theoretical foundation and practical guidance for CSC prevention and early warning.

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

Oil shale is a kind of high-combustion heat mineral, and its oxidation in mining and storage are worth studying. To investigate the low-temperature oxidation characteristics of oil shale, the temperature, CO, alkane and alkene gases were analyzed using a temperature-programmed device. The results showed that the temperature of oil shale underwent three oxidation stages, namely a slow low-temperature oxidation stage, a rapid temperature-increasing oxidation stage, and a steady temperature-increasing stage. The higher the air supply rate is, the higher the crossing point temperature is. Similar to coal, CO also underwent three stages, namely a slow low-temperature oxidation stage, a rapid oxidation stage, and a steady increase stage. However, unlike coal, alkane and alkene gases produced by oil shale underwent four stages. They all had a concentration reduction stage with the maximum drop of 24.20%. Statistical classification of inflection temperature of various gases as their concentrations change showed that the temperature of 140 °C is the key temperature for group reactions, and above the temperature of 140 °C, all alkane and alkene gases underwent the rapid concentration increase stage.

ABSTRACTThis paper investigated a slag composite high‐efficiency fire extinguishing material to recycle power plant slag waste and apply it to prevent and control spontaneous coal combustion fires. The composite uses power plant slag as a base material, sodium carboxymethyl cellulose (CMC) as a polymer, and AlCit solution formulated with polyaluminum chloride and citric acid as a cross‐linking agent. X‐ray diffractometer (XRD) and scanning electron microscope (SEM) were used to analyze slag composition and morphology. Experiments investigated the effects of composites on coal microactive groups, rheological properties, and inhibition characteristics against coal spontaneous combustion. Analyses showed composites could effectively reduce activities of aromatic hydrocarbons, OH groups, aliphatic hydrocarbons, and oxygenated functional groups in coal samples, with prominent inhibition of oxygenated functional groups and OH reactive groups. Experimental results showed composite samples exhibited a shear thinning phenomenon of yield‐pseudoplastic fluid, and viscosity gradually increased with time. Viscosity increase rates of samples were 9.20%, 17.35%, and 30.75% for each 5‐min interval. Composites could delay the time when coal samples enter the rapid oxidation stage, and the crossing point temperature of coal samples increased from 152°C to 180°C. Composites had an inhibitory effect on coal oxygen reaction, and in programmed warming experiments, the temperature at which the residual mass of coal samples began to increase increased from 179°C to 202°C. The slag composite high‐efficiency fire extinguishing material provides reference value for the combination of slag waste and mine fire extinguishing technology.

The iron(II)-activated peroxymonosulfate [Fe(II)/PMS] process is effective in degrading organic contaminants with a rapid oxidation stage followed by a slow one. Nevertheless, prior studies have greatly underestimated the degradation rates of organic contaminants in the rapid oxidation stage and ignored the differences in the kinetics and mechanism of organic contaminants degradation in these two oxidation stages. In this work, we investigated the kinetics and mechanisms of organic contaminants in this process under acidic conditions by combining the stopped-flow spectrophotometric method and batch experiments. The organic contaminants were rapidly oxidized with rate constants of 0.18-2.9 s-1 in the rapid oxidation stage. Meanwhile, both Fe(IV) and SO4•- were active oxidants and contributed differently to the degradation of different organic contaminants in this stage. Additionally, the presence of Cl- promoted the degradation of both phenol and estradiol but the effects of Br- and humic acid on phenol degradation differed from those on estradiol degradation in the rapid oxidation stage. In contrast, the degradation of phenol and estradiol was slow and the amounts of Fe(IV) and SO4•- generated were small in the slow oxidation stage. This work updates the fundamental understanding of the degradation of organic contaminants in this process.

As a new green chemical inhibitor, ionic liquids can inhibit spontaneous combustion of coal by dissolving and destroying the active structure in coal. In order to investigate the influence of ionic liquids with different concentrations on the molecular structure and the characteristics of low temperature oxidation kinetics of coal at oxygen-poor environment, taking Wucaiwan coal sample in Zhundong mining area as the research object, the molecular structure model of Wucaiwan coal in Zhundong mining area is constructed, and 1-(2-hydroxyethyl)-3-methylimidazole tetrafluoroborate [HOEtMIm] [BF4] ionic liquid is selected. The effect of ionic liquid on coal is investigated from macroscopic and microscopic levels by means of NMR carbon spectroscopy, X-ray photoelectron energy, infrared spectroscopy, thermogravimetry and X-ray diffraction. The results show that different concentrations of [HOEtMIm] [BF4] ionic liquids increase the ignition temperature point and the maximum weight loss rate temperature point of coal samples. The percentage of weight loss in the rapid oxidation stage and the whole combustion process of spontaneous combustion decreases with the increase of ionic liquid concentration. Compared with coal samples treated with other concentrations, the coal samples treated with 15% ionic liquids show good stability, and the fluctuation range of combustion characteristics parameters is small, which shows that high concentration ionic liquids can effectively reduce the influence of temperature on coal samples. Different stages of coal spontaneous combustion oxidation follow different reaction mechanism. The activation energy of the coal samples treated with different concentrations of [HOEtMIm] [BF4] ionic liquids did not change obviously in the evaporation and desorption stages of water, and the flame retardant effect was mainly shown in the oxygen absorption and weight gain stages and thermal decomposition stages. Higher concentration of ionic liquids can make aliphatic, oxygen-containing functional groups and side chains in coal structure fall off , so that the macromolecules of coal are arranged more closely, and the arrangement of organic carbon atoms tends to be oriented and regular gradually. The concentration of ionic liquids changed the polymerization degree of coal macromolecules, and the concentration of ionic liquids was proportional to the polymerization degree of coal macromolecules.

The stagnant water above the coal seam flows into the goaf, causing the goaf coal to be soaked by water for a long time. Compared with dry raw coal, water-soaked coal has a stronger tendency for spontaneous combustion, which poses a serious threat to mining operators. To unravel the impact of water immersion on coal's self-heating properties, an investigation was conducted employing techniques such as simultaneous thermogravimetric analysis/differential scanning calorimetry (TG/DSC), scanning electron microscopy (SEM), low-temperature nitrogen adsorption based on the BET theory, and Fourier transform infrared spectroscopy (FTIR). The variations in the characteristic temperature, microphysical structure, and active functional groups of bituminous coal with water immersion degrees of 10, 30, 50, and 100% were studied, and the experimental results showed that (1) during the initial stage of coal self-ignition oxidation, moisture can cause a delay in the characteristic temperature points of bituminous coal. When the degree of water saturation in bituminous coal reaches 100%, both the critical temperature (T 1) and the cracking temperature (T 2) peak at 48.14 and 205.06 °C, respectively. However, after the water evaporation phase is complete, water soaking promotes the spontaneous combustion of bituminous coal. (2) The number of pores and fractures in bituminous coal is positively correlated with the amount of water soaked, with the average pore diameter increasing from 10.124 nm in raw coal to 15.547 nm in the A4 coal sample. Moreover, when the degree of water immersion reaches 100%, the proportion of mesopores and macropores increases to 38.89 and 19.95%, respectively. (3) Compared to untreated coal, the number of functional groups in water-soaked coal samples increases. With the increase in water immersion, the hydroxyl (-OH) content of raw coal and four kinds of bituminous coal with different degrees of immersion was 40.8, 41.3, 42, 43.9, and 42.9%, respectively, showing a trend of increasing first and then decreasing. When the degree of water immersion of bituminous coal is 50%, the natural tendency is the strongest. These findings contribute to elucidating the underlying mechanism of water immersion's impact on coal self-ignition, thereby holding significant implications for enhancing fire safety measures in mine working areas.

Accurate prediction and forecasting are the important prerequisites for preventing and controlling the spontaneous combustion of coal. In this study, the production of CO, C2H4, C2H6, and other gases during the oxidation processes was studied by the temperature-programmed method with different particle sizes at a heating rate of 0.3°C/min and a dry airflow rate of 120 mL/min. Based on the quantitative relationship between the temperature and gaseous products, the index gases and their critical values at different oxidation stages were identified. By the gas growth rate method, the critical temperatures for the spontaneous combustion of the coal samples were determined to be in the range of 70°C ~ 80°C, and dry cracking temperatures were 130°C ~ 140°C. By the critical and dry cracking temperatures, the coal oxidation process was classified into three stages, the slow oxidation stage, rapid oxidation stage, and accelerated oxidation stage. A three-level early warning index for predicting coal spontaneous combustion quantificationally was proposed, including CO/CO2, CO2/O2, , and C2H4.

The intrinsic reaction of coal with oxygen in the process of low-temperature oxidation is the main reaction path leading to self-heating and spontaneous combustion of coal. Most of the existing studies regard the coal oxidation as an overall reaction, ignoring the multi-path characteristics of coal low-temperature oxidation, and it is difficult to accurately explore the intrinsic reaction characteristics between coal with oxygen. Therefore, the low-temperature oxidation process of coal was studied by using a C80 microcalorimeter and in situ FTIR technology from the macro and micro levels. The "profile subtraction method" was used to study the coal-oxygen intrinsic reaction process, and the reaction heat effect and the change characteristics of key functional groups in the process were analyzed. Furthermore, the gray correlation analysis method was used to study the relevant characteristic parameters in the reaction process and grasp the essential structure-activity relationship. The experimental results show that, compared with the overall reaction process in air atmosphere, the change in the heat release of the coal-oxygen intrinsic reaction path has changed to different degrees, and the change in the slow oxidation stage is the most significant (the heat absorption decreases by 70.1-90.9%). In addition, the characteristic temperature points show different degrees of advance, of which the initial exothermic temperature point is the largest (about 21-46 °C), which directly leads to a significant shortening of the slow oxidation stage (30.1-47.4%). The changes of functional groups in the intrinsic reaction path are more regular. With the increase of temperature, the oxygen-containing functional groups -C=O and the aliphatic hydrocarbon functional groups -CH2- and -CH3 showed a fluctuating trend of increasing and decreasing, respectively. The oxidation heat-contributing functional groups of coal are mainly related to the degree of metamorphism and the functional group reaction characteristics during the reaction. With the deepening of coalification degree, the main heat-contributing functional groups as a whole showed the change rule of oxygen-containing functional groups → aliphatic hydrocarbon functional groups → aromatic hydrocarbon functional groups. In addition, the change of -OH content in the three coal samples has a high correlation with the change of the total heat release of coal.

Insight into the influence of small organic molecules on the wettability of coal

Due to the complexity of the internal structure of natural coal and its characteristic of multicomponent, the depth of its methane adsorption potential well is nonuniform, which makes it difficult to accurately evaluate the adsorption capacity of coal. Besides, in order to find out the factors affecting the depth distribution of potential wells in natural coal, this paper calculated the depth and number of potential wells during methane adsorption in coal according to the Langmuir adsorption kinetics process. Coal samples with different metamorphic degrees were tested and analyzed by infrared spectroscopy diffraction technology. The relationship between the structural parameters of functional groups in coal samples with different metamorphic degrees and the distribution of different depths of adsorption potential wells in coal samples was studied. Some main conclusions are as follows: The number of adsorption potential wells at different depths in natural coal with different metamorphic degrees has multipeak distribution characteristics. With the increase of the metamorphic degree of coal sample, the structures such as aliphatic branched chain structure and oxygen-containing functional groups in coal structure break, fall off, and deoxygenate. The relative content of aliphatic hydrocarbons is significantly reduced and condensed into aromatic hydrocarbons and aromatic ring structures. The different types and quantities of functional groups on the surface of coal samples lead to different forces between coal molecules and methane gas molecules, thus affecting the distribution of different depths of adsorption potential wells in coal samples.