Spontaneous Combustion Tendency Research Articles

Evaluation Indicator for the Spontaneous Combustion of Biomass Fuel Pellets and Its Self-Ignition Control

ABSTRACT To investigate the spontaneous combustion characteristics of biomass fuel particles, spontaneous combustion processes of 10 biomass samples were simulated by programmed-heating and continuous oxidation experiments. Analysis results indicated that during the very initial stage of spontaneous combustion (<90 °C), each biomass fuel particles merely yielded CO at 0–20 ppm, while the subsequent exponential growth of gas emissions tended to exhibit a significant variation on spontaneous liability. Due to the diversity of biomass material sources, its spontaneous combustion tendency is not only determined by internal properties, but also influenced by external factors such as particle size, ventilation rate, moisture, etc. There are many factors affecting the spontaneous combustion tendency, which cannot be analyzed accurately and quantitatively. Therefore, it is necessary to propose a stable indicator based on thermal analysis to objectively evaluate the tendency of biomass spontaneous combustion. A scientific index was proposed to precisely assess the spontaneous combustion tendency of biomass materials. Specifically, the activation energy (E) at the O2 gain stage was adopted as the priority criterion: If E < 70 kJ/mol, the biomass was defined to be highly flammable; if 70 ≤ E ≤ 80 kJ/mol, the biomass was considered to be prone to self-ignition; and if E > 80 kJ/mol, the biomass was regard as non-spontaneous combustion. Besides, data from cross-point temperature tests fundamentally support the reliability of mentioned evaluation methodology. In fire-extinguishment experiments, a conventional approach, such as suffocate by self-extinguishing, only reduced the temperature to 99.9–238.7°C. The comparison of extinguishing materials such as gaseous N2/liquid nitrogen, CO2, and C3HF7 revealed that extinguishing fire with C3HF7 exhibited a dramatic advantage at burning temperature > 500°C. However, fire extinguishing with CO2 was more suitable for the spontaneous combustion ignition of biomass at temperature ≤ 300°C.

Analysis of temperature rise of low temperature adiabatic oxidation of sulfur-containing “coal-like substances”

ABSTRACT Spontaneous combustion of coal is one of the main natural disasters in the process of coal mining, and spontaneous combustion of sulfur-containing coal is an urgent problem to be solved. In order to understand the influence of different sulfur structures and sulfur content on spontaneous combustion tendency of coal, the self-developed synchronous temperature compensation adiabatic oxidation experiment system was used to study the oxidation self-heating performance of a series of sulfur-containing “coal-like materials.” Through the analysis of the heating rate of coal containing specific sulfur structure, it is considered that the time of adiabatic oxidation temperature of different organic sulfur “coal” to rise to 70°C is dimethyl sulfoxide > phenylene sulfide > dibenzothiophene. By analyzing the oxidation temperature rise characteristics of organic sulfur models with different sulfur contents, it is believed that the higher sulfur content, the faster the low temperature oxidation reaction of “coal-like substance,” the faster the temperature rise rate, and the shorter the time to reach the uncontrollable self-heating temperature, so the shorter the spontaneous combustion period. In general, in the stage of low temperature oxidation, active sulfur containing small molecules (dimethyl sulfoxide) promote the oxidation temperature rise, stable structure, larger molecular weight of dibenzothiophene slow down the “coal-like” oxidation temperature rise.

Experimental Study on the Inhibition Effect of the Inhibitor on Coal Spontaneous Combustion Under Critical Temperature.

At present, related research on inhibitors has been gradually improved, but there is still a lack of research on the inhibition characteristics at specific release temperatures and the mechanism of inhibiting coal spontaneous combustion. Based on this, In this study, the inhibition characteristics of adding inhibitor to coal under critical temperature (R70) are studied in depth. In the experiment, lignite was selected as the research object, and four different types of inhibitors, MgCl2, triphenyl phosphite (TPPI), Phytic acid (PA), and melatonin, were applied to coal samples at room temperature and 70 °C, respectively. The temperature-programmed-gas chromatography test and Fourier infrared spectroscopy experiment were carried out, and the oxidation kinetic parameters were calculated to study the oxidation characteristics and micromechanism of the coal samples in the process of spontaneous combustion. The experimental results show that the amount of CO gas release and oxygen consumption rate are lower, and the inhibition rate and apparent activation energy are higher when the inhibitor is added under R70 than at room temperature. Under R70, the content of oxygen-containing functional group -COOH with higher activity of inhibitor is reduced, the generation of active sites is inhibited, the concentration of active center is reduced, the path of mutual transformation between active sites and oxygen-containing functional groups is blocked, and the active groups are promoted to form a relatively stable inert oxygen-containing ether bond, which reduces the spontaneous combustion tendency of coal.

Study on the oxidized gas production characteristics and spontaneous combustion tendency of pre-oxidized water-soaked coal in lean-oxygen environments.

The oxidation characteristics and spontaneous combustion (SC) tendency of raw long-flame coal (RC), water-soaked 200-day coal (S200), pre-oxidized water-soaked coal at 200°C (O200S200), and pre-oxidized soaked coal at 300°C (O300S200) in an oxygen-poor environment were investigated using a programmed warming system. The results show that pre-oxidation water-soaked treatment (PWT) promotes the coal-oxygen complex reaction and increases the rate of coal oxygen consumption (OCR) and the rate of carbon and oxygen compound production. The rate of CO and CO2 production of the water-soaked (WS) coal increased by 0.329mol·(cm3·s)-1 and 0.922mol·(cm3·s)-1, respectively, compared with that of the original coal sample. PWT reduces the activation energy of coal in the low-temperature oxidation stage (the maximum difference can be up to 110.99kJ/mol) and enhances the oxidizing and heat-releasing capacity. There was a synergistic effect between the pre-oxidation (PO) and WS treatment, and the lowest comprehensive determination index of the SC propensity of coal in O200S200 samples was 831.92 which was 4.72 lower than that of RC samples, presenting a more SC tendency. Low oxygen concentration has an inhibitory effect on the oxidation characteristic parameters of coal, and the apparent activation energy of the low-temperature oxidation stage of pre-oxidized water-soaked coal (PWC) increased to 206.418kJ/mol at 3% oxygen concentration. The lower the oxygen concentration of the anoxic environment, the lower the risk of SC of the coal samples. The results of the study can provide theoretical guidance for the identification and prevention of SC disasters in coal seams with shallow burial and close spacing.

Effect of water immersion pressure on oxidation characteristics and spontaneous combustion characteristics of long-flame coal

Coal seam water injection has an obvious effect on coal dust prevention. The high-pressure water environment of coal seam water injection changes the structure of coal which brings new effects on the characteristics of coal spontaneous combustion disaster. To reveal the effects of water immersion pressure on the oxidation characteristics of long-flame coal, coal samples immersed in water at 0.1 MPa, 2.5 MPa, 5.0 MPa, 7.5 MPa and 10.0 MPa were prepared. Four experiments were conducted to study the changes in oxidation characteristics and its main reasons. The results showed that elevated water immersion pressure promoted the spontaneous combustion tendency of coal, and the composite judgment index of coal decreased to 521.1. Coal immersed in pressurized water entered the stages of oxygen-absorbing oxidation and thermal decomposition earlier than coal immersed in atmospheric pressure water. The specific surface area and average pore diameter of coal immersed in high-pressure water increased, where the pore volume proportion of mesopores of the coal immersed in water at 10.0 MPa increased by 138.5 % compared with that of the coal immersed in atmospheric pressure water. The elevated water immersion pressure prompted coal to produce further aliphatic hydrocarbons and hydroxyl groups, which improved the low-temperature oxidation capacity.

Time-shift effect of spontaneous combustion characteristics and microstructure difference of dry-soaked coal

The physical and chemical properties of the air-dried residual coal after soaking in the goaf will change, resulting in an increase in its spontaneous combustion tendency. This study aimed to look into the features and mechanism of soaked-dried coal's spontaneous combustion. Five samples of coal were dried to various degrees, and the weight loss features during thermal processing were examined. Based on this, the pore structure and chemical structure characteristics of the coal samples with the highest tendency to spontaneous combustion were quantitatively examined, and the mechanism by which soaking-drying affected the spontaneous combustion heating process of the remaining coal in goaf was investigated in turn. The results show that T1 decreases with the increase of drying time, T2–T6 shows a fluctuating change, and the ignition activation energy of 36-S-Coal is smaller than that of other coal samples. The pore type of 36-S-Coal changes from a one-end closed impermeable pore to an open pore, and the pore group area is large. During the 36 h drying process, the internal channels of the coal were dredged, and a large number of gravels and minerals were precipitated from the pores with the air flow. A large number of gravels were around the pores to form a surface structure that was easy to adsorb various gases. Furthermore, infrared spectroscopy was used to analyze the two coal samples. It was found that soaking and drying did not change the functional group types of coal samples, but the fatty chain degree of 36-S-Coal was reduced to 1.56. It shows that the aliphatic chain structure of coal is changed after 36 h of drying after 30 days of soaking, which leads to the continuous shedding of aliphatic chain branches of residual coal, and the skeleton of coal is looser, which makes the low-temperature oxidation reaction of 36-S-Coal easier. Based on the above results, the coal-oxygen composite mechanism of water-immersed-dried coal is obtained, and it is considered that the key to the spontaneous combustion oxidation process of coal is to provide oxygen atoms and accelerate the formation of peroxides.

Changes in the spontaneous combustion tendency of humic coals according to their petrographic composition and physico-chemical properties

Changes in the spontaneous combustion tendency of humic coals according to their petrographic composition and physico-chemical properties

Evaluation and Optimization of Multi-Parameter Prediction Index for Coal Spontaneous Combustion Combined with Temperature Programmed Experiment

Coal spontaneous combustion (CSC) is a serious threat to the safe mining of coal resources, and the selection of suitable gas indicators to predict the CSC state is crucial for the prevention and control of coal mine fires. In this paper, the temperature-programmed experiment of CSC was first carried out to analyze the gas components and compositions in the oxidative pyrolysis process of three coal samples (lignite, long-flame coal, and lean coal) with different coalification degrees. Subsequently, the spontaneous combustion tendency of these three coal samples was evaluated. Finally, through the variation of gas concentration, gas concentration ratio, and fire coefficient with coal temperature, the indicators suitable for predicting the spontaneous combustion of coal were preferred, and a multi-parameter indicator system was established to make a comprehensive judgment on the spontaneous combustion status of coal. The results show that coal rank is negatively correlated with oxygen consumption rate. The higher the coalification degree of coal, the slower the oxidation reaction and the later the characteristic temperature point appears. The lignite selected in this experiment is a type of coal that is more prone to spontaneous combustion than long-flame coal and poor coal, and the CO concentration, C2H6/CH4, and second fire coefficient R2 can be used as the main indicators for predicting CSC, while the other gases, olefin-alkane ratio and fire coefficient can be used as auxiliary indicators. To some extent, the research content can effectively and accurately determine the stage and degree of coal spontaneous combustion, which has a certain guiding role in predicting CSC.

Self-Healing Gels Based on Bimetallic ion Cross-Linking for Mining Fire Prevention and Extinguishing

ABSTRACT To address the environmentally friendly issue of fire prevention and extinguishing materials in coal mines, a new biomass gel material was prepared using sodium carboxymethyl cellulose (CMC) as the matrix, ferro aluminum citrate (Fe-AlCit) as the cross-linking agent, and gluconic acid-δ-lactone (GDL) as the pH modifier. Through performance tests of gel micromorphology, thermal stability, viscoelasticity and yield stress, it was found that the CMC-3 gel material with a ratio of 2.5% CMC + 4% Fe-AlCit +2% GDL had a dense surface structure, good thermal stability and moderate viscosity, which was the most suitable for pipeline transport. A metal coordination bond favorable to the stability of CMC-3 gel is formed by the carboxylate ion in CMC and the double high-valent metal ions Fe3+ and Al3+ dissociated by Fe-AlCit. CMC-3 gel exhibits excellent fire prevention and extinguishing properties. The results of the programmed warming experiments showed that the inhibition rate of the coal sample treated with CMC-3 gel against CO and C2H4 gases reached 44.84% and 46.57% at 220°C, respectively, and the growth rate of the activation energy in the first and second stage reached 17.63% and 22.68%, respectively, which plays a significant inhibitory role. The infrared spectroscopy test showed that after adding CMC-3 gel, the content of -OH and Ar-C-O in the coal samples was reduced by 49.58% and 40.82%, respectively, and the content of stable C=C in the aromatics was increased by 6.14%, which effectively blocked the coal-oxygen chain reaction and reduced the tendency of coal spontaneous combustion. The thermogravimetric test showed that the characteristic temperature points of the coal sample treated with CMC-3 gel were all increased to different degrees. The fire extinguishing test showed that CMC-3 gel could significantly reduce the temperature of coal sample and extinguish the coal fire quickly. Moreover, the CMC-3 gel material also has excellent self-healing properties, which can self-repair the damaged network through the abundant reversible hydrogen and ionic bonds inside the gel in only 90 s. The study has certain guiding significance for the development of efficient and environmentally friendly self-healing mining fire prevention and extinguishing materials.

Activated carbon modified by Mo-doped CQDs: An efficient method to reduce the thermal hazard in toluene adsorption

Activated carbon (AC) is one of the typical adsorbents for industrial treatment of VOCs, but AC itself has a high calorific value. When the heat generated by low-temperature oxidation cannot be released, it is easy to store heat and oxidize spontaneously, resulting in immeasurable harm. Therefore, it is important to study and improve the thermal stability of AC. In this study, Mo-doped carbon quantum dots (CQDs) was synthesized to enhance the safety of AC usage. The structure of AC before and after modification was characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffractometer (XRD). On the modified Mo-doped CQDs/AC, there are more crystalline structures formed by Mo oxides on the surface, which makes the intermolecular force on the surface of AC increase. At the same time, Mo oxide has strong oxidation resistance, which can inhibit the thermal decomposition process of AC, and has stronger stability. The spontaneous combustion tendency and thermal hazard of AC before and after modification were greatly improved. The heat released in the toluene adsorption by the modified AC at different temperatures was significantly lower than the heat released by the unmodified AC. According to the Langmuir adsorption isotherm, the adsorption performance of Mo-doped CQDs (2.5 wt%) was 1.6 times higher than that of AC when the system was 25 °C. The results showed that Na2MoO4 CQDs modified AC could effectively improve the thermal stability and greatly reduce the spontaneous combustion tendency. A relative fire safety performance evaluation model was also established to comprehensively evaluate the fire risk of VOCs treatment by AC.

Novel PFA-Based Inorganic Three-Phase Foam for Inhibiting Coal Spontaneous Combustion.

Fire accidents caused by coal spontaneous combustion usually lead to a large loss of coal resources and casualties. Not only that, the greenhouse effect is polluted while the environment is polluted. At present, the commonly used fire-extinguishing materials such as water, inhibitors, and organic foams have the disadvantages of poor stability and short fire-extinguishing cycles. It is difficult to effectively suppress coal spontaneous combustion and quickly extinguish the fire for a long time. To suppress the spontaneous combustion of coal, the research team proposed an inorganic three-phase foam with a high foam expansion rate, good cohesiveness, and excellent stability. In the formulation, pulverized fly ash (PFA) is used as the matrix, sodium dodecyl benzene sulfonate (SDBS) and α-olefin sulfonate (AOS) are used as foaming agents, curdlan is used as the foam stabilizer, and sodium silicate is the binder. The compound foaming agent with the best performance is optimized, through the two-group compounding test. The composite foaming agent's optimal compound ratio is SDBS/AOS (3:2). The optimal ratio of inorganic three-phase foam (ITPF) components was obtained through the control variable method experiment. The water-cement ratio is 5:1, the composite foaming agent is 0.2%, the curdlan is 0.5%, and the sodium silicate is 1.6%. In addition, it has been determined by experiments that ITPF has the strongest foaming ability when the pH value is 9 and the temperature is 60 °C. The fire-extinguishing performance of the new material ITPF was investigated by thermogravimetry and coal spontaneous combustion tendency test. It has been observed that the new material has the effect of cooling down and isolating coal from contact with oxygen. The results show that the new material ITPF has the potential to prevent coal spontaneous combustion.

Experimental study of microbial desulphurisation of sulphide ores combined with gel foam retardants to prevent spontaneous combustion

ABSTRACT The purpose of this study was to reduce the propensity for spontaneous combustion of sulfide ores through the combined action of microorganisms and inhibitors and to assess the flame retardant effect. The sulfide ore samples were first pretreated with biodesulphurisation. The samples were then sprayed with a foam blocker to prevent re-oxidation of the ore and further reduce the spontaneous combustion tendency of the sulfide ore. The experimental results showed that the highest desulfurization rate of 24.26% was achieved for ore samples with a particle size between 140–160 mesh. A combination of 0.05% hexadecyltrimethylammonium bromide (CTAB), 0.11% lauramidopropyl betaine (LAB-35), 0.13% sodium alcohol ether sulfate (AES), 0.11% propanetriol foam stabilizer, 7% water glass and 3% sodium bicarbonate arresting agent was the most effective. The oxidation weight gain of the desulphurised ore sprayed with the resist was only 3.16%. The oxidation weight gain of the desulphurised ore without the addition of the resist was 3.98% and the oxidation weight gain of the undesulphurised ore was 6.01%. This method is effective in reducing the tendency of spontaneous combustion of sulfide ores.

Experimental Study on Catalytic Action of Intrinsic Metals in Coal Spontaneous Combustion.

In order to study the effect of inherent metals in coal on spontaneous combustion, Hongmiao lignite and Hongqingliang long-flame coal were demineralized by hydrochloric acid, the raw coal and demineralized coal were characterized by Fourier transform infrared spectrometry, X-ray diffraction, and synchronous thermal analysis experiments, and the corresponding ash content was detected by inductively coupled plasma mass spectrometry. The results show that the effect of demineralization on the volatile matter of low-rank coal is small, and the change of crystallite structure is not significant. The removed parts are mainly water-soluble salts and soluble minerals, such as carbonates and metal ions, that are not tightly bound to the organic matter of coal structure. The removed metal elements are mainly alkali metals Na and K, alkaline earth metals Ca, Mg, Sr, and Ba, and transition metals Fe, Mn, Ti, and so forth. The temperatures corresponding to the end of weight loss, ignition, and maximum weight loss rates were elevated on the thermogravimetric curves of the demineralized coal samples. The heat absorbed by evaporation of water in coal and the heat released by oxidation and combustion of coal are decreased to different degrees, indicating that the spontaneous combustion tendency of coal after demineralization is reduced, and alkali metal, alkaline earth metals, and transition metals in coal have a catalytic effect on spontaneous combustion of coal. After adding the metal chelating agent ethylenediaminetetraacetic acid (EDTA), the apparent activation energy decreased by 33.08 and 2.42%, respectively. EDTA and the alkali metal, alkaline earth metal, or transition-metal ions formed a stable chelate in coal. The catalytic activity of metals is weakened or even lost, thereby inhibiting spontaneous combustion of coal, and verifying the catalytic effect of internal metals in coal on the spontaneous combustion of coal.

Analytical Prediction of Coal Spontaneous Combustion Tendency: Pore Structure and Air Permeability

In previous research, many scientists and researchers have carried out related studies about the spontaneous combustion of coal at both the micro and the macro scales. However, the macroscale study of coal clusters and piles cannot reveal the nature of oxidation and combustion, and the mesoscale study of coal molecule and functional groups cannot be directly applied to engineering practice. According to our literature survey, coal is a porous medium and its spontaneous combustion is a multi-scale process. Thus, the mesoscale study of coal’s spontaneous combustion is essential. In this manuscript, the mesoscale of the coal body (such as pore size, pore volume, and specific surface area), and the meso-scale structural morphological characteristics of the coal surface are finely analyzed and characterized. On this basis, the meso-scale structure of pores and fractures are digitally reconstructed. Furthermore, velocity and pressure distributions of the flow field in the pores of the scan plane are outlined and described by numerical simulation. The results indicate that, because of the pore structure characteristics and fluid viscosity, not all fluids in the pores demonstrate flow. This conclusion well explains the source of CO gas in methane extraction pipes, which is one of the main index/indicator gases of the spontaneous combustion of coal.

Spontaneous Combustion Characteristic Stages of Active FeS and Its Inhibition Effect by Gas-Phase Passivation

ABSTRACT To explore the spontaneous combustion characteristic stages of active ferrous sulfide (FeS) and its inhibition effect by gas-phase passivation. Active FeS samples were prepared and then the spontaneous combustion characteristics of active FeS and commercial FeS samples were compared. The active FeS spontaneous combustion process was divided into several characteristic stages from the perspective of spontaneous combustion kinetics. Furthermore, the inhibition effect of gas-phase passivation on the characteristic stages and the kinetics and thermal effects of active FeS spontaneous combustion process were investigated to further reveal the inhibition mechanism. The results indicate that spontaneous combustion process of active FeS is divided into the room temperature (RT) spontaneous combustion, oxygen-adsorption-induced weight gain, high-temperature combustion and burnout stages, while the spontaneous combustion process of commercial FeS excludes the RT spontaneous combustion stage. Active FeS presents greatly advanced characteristic stages, stronger spontaneous combustion reactivity and more intense reaction in the RT spontaneous combustion and high-temperature combustion stages, which agrees more with the sulfur corrosion products under actual on-site working conditions. The spontaneous combustion tendency of passivated FeS weakens gradually with the increase of passivation time until it loses its RT spontaneous combustion reactivity after 6 h passivation. After the oxide film formed on the surface of passivated FeS is destroyed, its high-temperature combustion reaction becomes relatively intense. The activation energy of passivated FeS in the spontaneous combustion reaction is much higher than that of active FeS, and their activation energies both soar with the deepening of passivation, indicating that the gas-phase passivation technology can effectively inhibit the FeS spontaneous combustion process. The gas-phase passivation time must be maintained for over 6 h despite the weakening inhibitory effect of passivation treatment on the FeS spontaneous combustion process.

Combustion performance of lignite after efficient upgrading via deep eutectic solvent‐assisted hydrothermal dewatering

AbstractIn order to increase the efficiency of hydrothermal dewatering (HD), a deep eutectic solvent (DES, synthesized by ChCl and ZnCl2) was employed to promote the removal of moisture and oxygen from lignite. The variation of physicochemical structure of upgraded coals greatly affected the combustion performance. The effects of addition amount of DES, upgrading temperature, and the molar ratio by ChCl and ZnCl2 on combustion performance of upgraded coals were analyzed via thermogravimetric analysis. Compared with HD lignite upgraded at 280°C, the combustion curves of DES‐HD lignite were shifted and delayed toward a higher temperature zone as DES additions increased. DES‐HD lignite had lower spontaneous combustion tendency and higher combustion reactivity. When upgrading temperature increased from 250 to 300°C, the combustion curves of lignite upgraded with 3.0‐g DES (ChCl:ZnCl2 = 1:1) first moved to the low‐temperature zone and then shifted to the high‐temperature zone. DES‐HD lignite maintained the advantages of raw coal in terms of combustion characteristics. For lignite upgraded with different molar ratios of ZnCl2 in DES, the difference in combustion behavior was mainly manifested in the burnout stage. The burnout stage was advanced slightly as the molar ratio of ZnCl2 increased.

Study on dominant structural factors and laws of combustion performance of acidified coal

The application of acidification technology changes the pore structure and microcrystalline structure of coal, which affects the combustion characteristics of coal products. In this study, three inorganic acids (HF, HCl, and HNO3) were used to treat bituminous coal, and low-temperature nitrogen adsorption tests, X-ray diffraction analysis (XRD), and simultaneous thermal analysis (STA) were carried out. Fractal dimension theory, microcrystalline structure analysis theory, and thermal analysis kinetic theory analyze the pores, crystallites, and combustion characteristics of raw coal and acidified coal, respectively. The correlation between variables can be judged by the Pearson correlation coefficient. The research results show that compared with the microcrystalline structure, the pores determine the acidified coal's synthetical combustion index S, maximum value of differential thermal analysis DTAtop and maximum mass loss rate dW/dtmax to a greater extent. Hydrofluoric acid increased the average pore size of the raw coal by 38.66%, resulting in an 11.60% increase in dW/dtmax. The ignition temperature T5 is the composite performance of the aromatic structure's thermal stability and the microcrystalline structure's ordering. The aromaticity fa determines the reaction in the oxidation weight gain stage to a greater extent and can be used as a new indicator to characterise the spontaneous combustion tendency of coal. The pore and microcrystalline structures jointly determine the activation energy E3 in the combustion stage.

Experimental study of moisture effects on spontaneous combustion of Baiyinhua lignite from individual particles to stockpile

Evaporation and condensation of moisture affect dramatically the spontaneous combustion of lignite with high moisture content at low temperatures. Moisture migration between the lignite and the external environment of coal stockpile encompasses the scales of individual particles and stockpile. The cyclic moisture evaporation/condensation test was applied to investigate moisture migration of individual lignite particles at different particle sizes and temperatures. The wire-mesh basket test was selected primarily to analyze the heating process and critical self-ignition temperature of lignite stockpile. Results of the cyclic moisture evaporation/condensation test reveal that the moisture content of re-saturated lignite is much lower than that of the original one. Moisture content versus time showed a tendency to overlap in repeated moisture evaporation processes, and so did the repeated moisture evaporation processes. Therefore, a model of moisture migration of individual particles was built to describe the repeated moisture evaporation and condensation processes. The time factor determines the speed of moisture evaporation and condensation of individual lignite particles, being inversely proportional to ambient temperature and proportional to particle size, respectively. In the wire-mesh basket test, the heating process of the lignite stockpile can be divided into four stages, but the influence of moisture was more pronounced in stage II. Critical self-ignition temperature is proportional to particle size and increases linearly with moisture content. According to Frank-Kamenetskii theory, an increase in either particle size or moisture content can restrain the tendency of spontaneous combustion of Baiyinhua lignite stockpile.

Influence of Organic Sulfur on Low-Temperature Oxidation of Coal and its Transition Characteristics.

The low-temperature oxidation spontaneous combustion of coal was caused by the active groups in its structure. The oxidation mechanism of carbon and oxygen functional groups in coal had been extensively studied, but there were few reports on the study of sulfur functional groups initiating the coal spontaneous combustion. To investigate the influence of organic sulfur functional groups on the spontaneous combustion of high-sulfur coal and explore its transformation characteristics, the low-temperature oxidation experimental system was used to study the spontaneous combustion tendency of coal with similar metamorphic degrees and different organic sulfur contents. The variations of element forms and organic sulfur functional groups were analyzed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy during low-temperature oxidation of coal and model compounds. The results showed that the forms of organic sulfur in coal mainly included mercaptans, thioethers, thiophenes, sulfones (sulfoxides), and sulfates, and the low-temperature oxidation of coal was not only related to the content of organic sulfur but also related to its type. The coal samples, which possess a low content of total sulfur and a small proportion of active organic sulfur groups such as mercaptans and thioethers, had a lower concentration of indicator gas and a smaller tendency to coal spontaneous combustion. After low-temperature oxidation, the content of mercaptan, thioether, thiophene, methyl(methylene), and pyridine in coal decreased, and the content of oxygen-containing groups such as sulfone (sulfoxide), sulfate, carboxyl, and nitrogen oxide increased. The elements of S, C, and N all changed to a high-valent state. In the oxidation reaction of model compounds, mercaptans were more reactive than thiophenes in the low-temperature region, and the oxidation of thiophene could direct form sulfone (sulfoxide), while the oxidation of mercaptan formed disulfide first. It is speculated that low-valence sulfur migrated to a high-valent state by providing sulfhydryl radicals (•SH) and sulfur radicals (C-S•) combined with active oxygen atoms. After the low-temperature oxidation reaction of model compounds, some organic sulfur existed in the form of aromatic sulfur or sulfur oxides and a small part of sulfur escaped as SO2 and H2S gases in the solid oxidation product.

Interaction Study of Oxygen and Iron-Sulfur Clusters Based on the Density Functional Theory

For the petrochemical industry, the spontaneous burning of iron sulfide compounds has been a major issue. In this study, XRD characterization of samples of iron sulfide compounds with spontaneous combustion tendency revealed that amorphous FeS was the primary constituent of the samples. A molecular simulation was used to build an amorphous FeS cluster model, and the density functional theory was used to examine the adsorption and reactivity characteristics of Fe4S4 clusters with O2. Different adsorption structures are generated by considering different adsorption sites and the electronic characteristics of each adsorption structure are evaluated. The results show that O2 prefers to adsorb around Fe atoms and has repulsion with S atoms, and the adsorption energy is maximum when two O atoms are co-adsorbed around Fe atoms, which is 198.13 kJ/mol. After adsorption charge, oxygen is in the superoxide state. The calculation of the reaction path divides the reaction process into different stages and considers different reaction routes. A thorough evaluation of the energy barriers and reaction energies of the two exothermic reactions leads to the conclusion that reaction path 1 is the optimal reaction path, and the reaction can release a total of 582.76 kJ/mol of heat. According to calculations, dimeric sulfur S2 must absorb a large part amount of energy in order to conduct the oxidation process. However, because S2 is present in the Fe4S4 reaction system, it may start the oxidation reaction by absorbing heat from the system and releasing 470.94 kJ/mol of heat. As a result, we conclude that this spontaneous exothermic reaction is a major cause of iron sulfide compounds spontaneous combustion. The thermal oxidation of the dimeric sulfur S2 generated in the reaction system releases heat that aggregates with the heat from the Fe4S4 cluster’s oxidation reaction system, eventually causing spontaneous combustion as a result of the heat’s continual buildup. In this study, we explore the reason for the extremely easy oxidation and spontaneous burning of iron sulfide compounds from a microscopic perspective to provide a theoretical foundation for the prevention and control of iron sulfide compound spontaneous combustion in the petrochemical sector.