The effect of N2/CO2 blend ratios on the pyrolysis and combustion behaviors of coal particles: Kinetic and thermodynamic analyses

The aim of this work is to investigate the impact of various CO₂/N₂ ratios on coal pyrolysis and combustion properties and to provide theoretical guidance for better preventing and controlling coal spontaneous combustion in the goaf. The dynamic pyrolysis and combustion characteristics of DX coal were analyzed by using a thermal gravimetric analyzer (TGA) in a constant oxygen atmosphere with different CO₂/N₂ blend ratios. The Málek method combining Coats-Redfern and Achar methods was used to determine the most probable mechanism functions. CO₂ containing atmospheres increased characteristic temperatures, burnout rate, maximum mass loss rate and comprehensive combustion performance index compared to O₂/N₂ atmospheres. In stages I-III, a lower apparent activation energy was observed in O₂/CO₂ atmospheres. Apparent activation energy and enthalpy changes showed upward trends in the reaction stage (I→III→IV), whereas Gibbs free energy change and entropy change decreased. The dynamic pyrolysis and combustion of DX coal necessitated increased energy in environment with a CO₂/N₂ ratio of 4:6, revealing the optimal inhibitory effect on DX coal with this particular ratio.     

The influence of oxygen concentration on the composition of gaseous products occurring during the self-heating of coal and wood sawdust

This article deals with an assessment of the influence of oxygen concentration on the composition and amount of combustion products generated in the course of heating coal particles and wood sawdust at 150 °C. This was done both with normal air and at 15% oxygen in the air in an isothermal furnace. The generated gases were analyzed by a Fourier Transform infrared spectrometer. Results show that under both conditions, the same substances are formed: water, carbon dioxide, carbon monoxide and aliphatic hydrocarbons. However, the quantities changed. At 21% oxygen, the concentrations of carbon monoxide and methane were higher than at 15% oxygen both in coal and wood. The oxygen concentration was also found to affect the rates of release of CO and CO₂. The rate of release of CO was higher at 21% oxygen, but that of CO₂ was higher at 15%, indicating two different mechanisms. In all cases, the concentrations of these gases were higher for coal than for wood. The results have implications for the specification of safe conditions of storage of coal and wood substances and the selection of safety measures.     

Corrosion behavior of steels for CO2 injection

The process chain for Carbon Capture and Sequestration (CCS) includes tubing for injection of CO₂ into saline aquifers. The compressed CO₂ is likely to contain specific impurities; small concentrations of SO₂ and NO₂ in combination with oxygen and humidity are most harmful. In addition, CO₂ saturated brine is supposed to rise in the well when the injection process is interrupted. The material selection has to ensure that neither CO₂ nor brine or a combination of both will leak out of the inner tubing. In this comprehensive paper the investigated materials range from low-alloy steels and 13% Cr steels up to high-alloy materials. Electrochemical tests as well as long term exposure tests were performed in CO₂, in brine and combination of both; pressure was up to 100 bar, temperature up to 60 °C. Whereas the CO₂ stream itself can be handled using low alloy steels, combinations of CO₂ and brine require more resistant materials to control the strong tendency to pitting corrosion. The corrosion behavior of heat-treated steels depends on factors such as microstructure and carbon content. For different sections of the injection tube, appropriate materials should be used to guarantee safety and consider cost effectiveness.     

煤自燃灾害气体指标的阶段特征试验研究

为分析煤自燃早期气体指标变化特征规律,更好地解决煤矿现场灭火救灾决策问题,通过煤自燃程序升温试验,首先得到煤样气氛中O2,CO,CO2,CH4,C2H4和C2H6气体的体积分数随温度的变化规律。根据煤体温度,将煤自燃前期划分为5个阶段(潜伏、储热、蒸发、活跃和乏氧)。分析3种不同变质程度的煤样的气体指标在各阶段的变化特征。建立煤自燃气体指标与特征温度阶段区间的对应关系。结果表明:在自燃潜伏阶段,煤的变质程度越低,早期越易产生CO,越难产生CH4;在储热阶段,煤的变质程度越低,早期越易且越快产生C2H6;在蒸发阶段,煤内外在水分脱附,低变质煤的C2H4也随之产生;在活跃阶段,各种气体体积分数均有剧烈增高的趋势,较高变质煤的C2H4也随之产生;在乏氧阶段,O2体积分数低于15%,与O2体积分数相关指标(CO/ΔO2,CO/CO2等)趋势有所改变。     

煤炭自燃倾向性试验研究及指标气体优选

通过对新鲜煤样和氧化煤样的热解实验,研究萍乡矿业集团某煤矿煤自燃发火特性,测定实验煤样在不同热解温度下O2,N2,CO,CO2等及其他碳氢化合物的浓度,具体分析了O2,CO,CO2,CH4,C3H6浓度随温度变化特性。在实验和研究的基础上,结合指标气体选择的一般原则,讨论了用于萍乡矿业集团某煤矿预测、预报煤炭自燃发火的指标气体,对提高煤炭早期自燃预测、预报的准确度和防止矿井火灾有重要指导意义。     

Experimental study on the minimum explosion concentration of anthracite dust: The roles of O2 mole fraction,inert gas and CH4 addition

The explosion characteristics of anthracite coal dust with/without small amount of CH₄ (1.14 vol %) were investigated by using a 20 L spherical explosion apparatus with an emphasis on the roles of oxygen mole fraction and inert gas. Two methods based on overpressure and combustion duration time were used to determine the minimum explosion concentration (MEC) or the lower explosion limit (LEL) of the pure anthracite coal dust and the hybrid coal-methane mixtures, respectively. The experiment results showed that increasing oxygen mole fraction increases the explosion risk of coal dust: with increasing oxygen mole fraction, the explosion pressure (P_ex) and the rate of explosion pressure rise ((dp/dt)_ex)) increase, while MEC decreases. The explosion risk of anthracite dust was found to be lower after replacing N₂ with CO₂, suggesting that CO₂ has a better inhibition effect on explosion mainly due to its higher specific heat. However, the addition of 1.14% CH₄ moderates the inhibition effect of CO₂ and the promotion effect of O₂ on anthracite dust explosion for some extent, increasing explosion severity and reducing the MEC of anthracite dust. For hybrid anthracite/CH₄ mixture explosions, Barknecht's curve was found to be more accurate and conservative than Chatelier's line, but neither are sufficient from the safety considerations. The experimental results provide a certain help for the explosion prevention and suppression in carbonaceous dust industries.     

不同粒径易自燃煤常温氧化实验研究*

为探究易自燃煤在常温条件下的氧化特性,自行设计煤常温封闭氧化实验装置,采用实验研究与回归分析2种方法,分析易自燃煤发生氧化反应的气体变化过程,探究3种粒径煤样在20 ℃有限空间内的耗氧与产气特征。结果表明:易自燃煤样在16 d常温封闭氧化过程中,容器内O2体积浓度呈指数衰减、CO和CO2体积浓度呈指数增长的变化规律;在0.06~0.83 mm范围内,粒径越大,易自燃煤耗氧速率越大,CO和CO2产生速率则先增大后减小;介于中间的粒径为0.13~0.25 mm易自燃煤氧化反应最强烈,更容易发生氧化。研究结果对揭示生产环境温度下煤粒粒径对煤自燃的影响有一定的意义。     

Effect of particle size on CO adsorption and thermodynamic analysis

The liquid nitrogen adsorption method was used to characterize the pore structure of non-cohesive coal in the 061,404 working face of the Lingxin coal mine. The amount of specific surface area of micropores in the sample continuously rose as particle sizes reduced. The volumetric method was used to measure the CO isothermal adsorption curves of three samples (sample I, 0.425–0.25 mm, sample II, 0.18–0.25 mm, and sample III, 0.15–0.18 mm). The experimental results were fitted by the Langmuir model. According to the experimental results, it was conducive to CO adsorption with the conditions of high pressure and low-temperature. The decrease in grain diameter increased the number and volume of micropores in the sample, which improved the adsorption capacity of the sample. In addition, according to the adsorption data, the CO adsorption thermodynamics of three samples were analyzed, including surface potential (Ω), Gibbs free energy change (ΔG) and entropy change (ΔS). The results demonstrated that CO adsorption by coal was a spontaneous process. Sample III has the most substantial adsorption capacity, whereas the sample I has the weakest adsorption capacity.     

Sources of underground CO: Crushing and ambient temperature oxidation of coal

As a harmful gas in underground coal mine, CO seriously threatened the safety of miners. Currently, the spontaneous combustion of residual coal in goaf is generally considered as the main source of underground CO. CO gas is also widely used as an indicator gas in fire prediction in mines. However, high concentrations of CO are also detected in some mines without spontaneous combustion of coal. Therefore, in the paper, with four ranks of coal, we studied other two potential CO sources: crushing and oxidation at ambient temperature. The more completely crushed coal produces more CO. The concentration of generated CO is inversely proportional to moisture content in coal. Therefore, the addition of water can inhibit the generation process of CO during the crushing process of coal. Lignite with low metamorphic grade can be oxidized to produce CO at ambient temperature (25 °C), and anthracite with high coal rank can be only oxidized to produce CO at 60 °C. Infrared spectra indicated that the coal with rich aliphatic hydrocarbons and oxygen-containing functional groups are more susceptible to oxidation at room temperature. Moreover, the smaller particle size of coal is more beneficial to the oxidation at ambient temperature to generate CO. CO generation during coal oxidation is also closely related to the ventilation rate.     

Effect of superfine KHCO3 and ABC powder on ignition sensitivity of PMMA dust layer

In order to evaluate the flame-retardant capacity of KHCO₃ and ABC on the ignition of PMMA dust layer accumulation on hot surfaces, the ignition time and critical heating temperature of PMMA/KHCO₃ and PMMA/ABC dust layer were experimentally investigated. The thermal stability of the mixed dust, the condensed phase products and gas phase products of the mixed dust combustion were analyzed to reveal the flame-retardant mechanism. The ignition time of 30 μm PMMA was obviously longer than that of 5 μm PMMA, and the critical heating temperature was close to that of 5 μm PMMA. KHCO₃ and ABC could greatly extend the ignition time of the PMMA dust layer and increase the critical heating temperature of the dust layer. ABC was more effective than KHCO₃. The decomposition of KHCO₃ and ABC absorbed the heat and inhibits the pyrolysis of PMMA. The HPO₃ and P₂O₅ generated by the decomposition of ABC would cover the surface of PMMA aggregates or particles and act as a physical barrier. The main light combustible gas produced by PMMA pyrolysis were CO and C₂H₄. The CO₂ generated during the decomposition of KHCO₃ could dilute the combustible gas in the ambient to inhibit the combustion of PMMA.     

煤自燃发火潜伏期不同温度下耗氧特性的研究

为了探究地层温度的升高对采空区自燃倾向性的影响,对处于自燃潜伏期的煤展开耗氧特性和CO释放特性的研究。通过对长平矿3#煤分别进行20~60℃的封闭耗氧实验,得到了自燃潜伏期不同温度下煤的氧浓度以及CO浓度随时间变化的曲线。对氧浓度变化曲线和CO浓度变化曲线进行拟合分析得到了不同温度下煤的氧气消耗和CO生成速度,同时得到了氧浓度衰减系数和CO浓度增长系数。封闭耗氧实验结果表明:从20~60℃氧气消耗速度逐渐增大并且氧浓度衰减系数呈指数增长,CO浓度增长系数也逐渐增大并且同样呈指数增长,煤的窒熄带氧浓度临界值从20~60℃逐渐由16.8%降低到12.4%。为探究不同温度下采空区煤的自燃发火危险性,将封闭耗氧实验结果的参数应用到采空区CFD数值模拟仿真中,模拟得到随着温度升高采空区窒熄带临界氧浓度位置由200 m增长到380 m。结果表明:常温下不易自燃的煤在较高的环境温度下表现出了较强的氧气消耗和CO释放能力,并且采空区自然氧化带随着温度的升高动态变宽,增大了采空区的自燃发火危险性。     

Fracture criterion and control plan on CO2 pipelines: Theory analysis and full-bore rupture (FBR) experimental study

Pressurized pipelines are the most reliable and cost-effective option for the long-distance transportation of CO₂ from an emitter to an onshore storage site. Propagating or unstable factures are considered catastrophic pipeline failures, resulting in a massive escape of inventory within a short period of time. The decompression curve for CO₂ exhibits a large drop in decompression wave speed at the phase transition pressure, leading to a higher driving force for crack propagation. The study of fracture control plans is very important for assessing the possibility of fracture propagation and preventing unstable fracturing along CO₂ pipelines. Three full-bore rupture (FBR) experiments were performed using an industrial-scale (258 m long, 233 mm inner diameter) CO2 pipeline with initial CO2 states of gaseous, dense and supercritical phases, respectively. The relation between the decompression velocity and the pipeline fracture propagation velocity was analyzed during the process of buried CO2 pipeline release. A fracture propagation criterion was established for the buried CO₂ pipeline. For the gaseous CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity only appeared near the closed end of the pipeline. For the dense CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity was observed near the saturation pressure after rapid decompression. For the supercritical CO₂ leakage, the pressure plateau corresponding to the decompression wave velocity was observed in the stage when the supercritical CO₂ transformed into the two phases of gas and liquid. Compared with the gaseous and dense CO₂, for the supercritical CO_2, the initial decompression wave velocity was the smallest, and the requirement of the pipeline safety factor was the highest.     

不同煤层煤氧化自燃性实验分析

为研究不同煤层煤自然发火特征的异同性及规律,以淮南矿区1号、3号、6号、13号煤层为研究对象,通过自然发火实验,对不同煤层煤的自然发火期周期、煤样70℃时放热强度和R70值进行分析。研究结果表明:4个不同煤层煤样自燃性由强到弱依次为:3煤>6煤>1煤>13煤;变质程度相近的4个煤层,3煤自然发火期最短,这与煤体中硫分和水分含量高有关;13煤变质程度较高,且前期放热强度、耗氧速率增长缓慢,其自燃性较弱;4个不同煤层煤的耗氧速率、CO,CO2产生率,以及C2H4/C2H6值随煤温升高具有相似的变化规律;煤中CH4气体大量解吸出现于煤温60℃之前,煤中灰分在80~120℃开始逐渐吸热融化,解析和融化均会抑制煤氧接触并且减小煤氧反应放热总量。     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

The relationship between oxygen consumption rate and temperature during coal spontaneous combustion

Spontaneous combustion is a major natural disaster in coal production. In the process of exploring coal self-ignition, a series of hypotheses have been put forward, most scholars agree that the current coal-oxygen compound theory. Oxygen consumption rate reflects the status of coal spontaneous combustion, and it is also one of the parameters necessary for numerical simulation of coal spontaneous combustion. In this paper, a coal heating and oxidation experiment was designed, Experimental device consists of heating and oxidation furnace, gas chromatograph, temperature control and data acquisition systems and other equipment components. Three coal samples whose weight each is 5 g were selected for the study. By experiment, oxygen concentration at the inlet and outlet of temperature oxidation furnace was measured. Oxygen consumption rate is calculated in the heating process of coal according to air flow. In the Cartesian coordinate system, the temperature as abscissa and the oxygen consumption rate for the longitudinal coordinates, drawing the relationship between oxygen consumption rate and temperature plot. And then regression analysis was used to analyze the relationship between oxygen consumption rate and coal temperature during the heating and oxidation process of coal. The results show that the oxygen consumption rate and temperature of coal were linear relationships both before and after the critical temperature when the coal temperature is less than 180 °C. Before the critical temperature oxygen consumption rate is low, however it increases rapidly when coal temperature reaches a critical temperature. The result is important for the prevention and treatment of spontaneous combustion of coal.     

水化煤饱和-风干过程的自燃特性实验研究

为了掌握水化煤饱和-风干过程中不同风干时间煤样的自燃特性,对水化煤样进行不同风干时间的实验煤样预处理,形成不同风干时间的水化煤样。通过煤样含水率测试、物理吸附实验和程序升温实验,对不同饱和-风干时间的水化煤样以及原煤样的吸氧量和CO,CO2,CH4,C2H4,C2H6,C3H8气体浓度随煤温的变化规律进行实验研究。研究结果表明:不同风干时间水化煤样随着煤温的逐渐升高,吸氧量呈先减小后增大趋势;不同风干时间的水化煤样的自燃标志性气体析出速率随煤温的升高均呈指数增大的变化趋势;在低温氧化阶段,水化煤样比原煤反应时间提前,且反应速率更快,这表明水化煤样比原煤样更加容易发生自燃,且风干时间为20 min的水化煤危险性更大。     

基于惰化降温耦合作用的采空区低温CO2注入位置研究

为了更好的使用低温CO2预防采空区煤自燃事故,利用FLUENT数值模拟的方法,结合宣东二号煤矿Ⅲ3煤层209工作面的实际条件,构建了考虑采空区不同压实程度的低温CO2注入采空区惰化降温耦合作用数值计算模型;分别研究了CO2注入量为540m3/h和720m3/h时,不同注入位置对采空区氧化带内最高温度点和氧化带宽度变化的影响。研究表明,合理的低温CO2注入位置为距工作面支架尾梁20～30m。     

The effect of ventilation on spontaneous heating of coal

Ventilation plays an important role in the spontaneous heating of coal in an underground coal mine. If the ventilation rate is too high, heat is carried away by convection. If the ventilation rate is too low, the reaction rate becomes oxygen-limited. The effect of ventilation on the spontaneous heating of coal was investigated in an isothermal oven in this study. Experiments were conducted on three U.S. coal samples with ventilation rates ranging from 100 to 500 cm³/min. Experiments under ventilation were conducted to determine the critical ambient temperature, which is the minimum oven temperature required for a coal sample to achieve thermal runaway. Spontaneous heating tests were then conducted at various ventilation rates at the critical ambient temperature and the results were compared with spontaneous heating tests without ventilation. It was found that there is an optimum ventilation flow to produce the maximum rate of temperature rise at the critical ambient temperature. When the coal sample particle size was increased, a higher critical ambient temperature was required. The results in this study have application in the prevention of spontaneous combustion in underground coal mines.     

CO在烟煤中吸附与扩散的分子模拟研究*

为揭示CO在烟煤中的微观吸附和扩散机理,利用Wiser烟煤分子模型,通过巨正则蒙特卡洛（GCMC）和分子动力学方法,研究5种不同温度（293.15,303.15,313.15,323.15,333.15 K）下,压力为0.1～3.0 MPa时CO吸附量、吸附热的变化,采用能量分布分析CO在烟煤中的吸附行为,利用扩散系数和扩散活化能研究CO在烟煤中的扩散特性。研究结果表明:CO在烟煤分子中的模拟结果符合朗格缪尔（Langmuir）吸附规律,随着温度的升高,Langmuir参数a和b减小,CO在烟煤分子中饱和吸附量和吸附能力降低。温度越高,烟煤分子的等量吸附热越低,烟煤分子吸附CO分子的平均等量吸附热为21.20～23.11 kJ/mol,小于42 kJ/mol,属于物理吸附;随着压力的升高,CO分子由能量较高的优势吸附位点逐渐向相对较弱的吸附位点移动;在模拟的温度和压力条件下,CO在烟煤分子模型中的扩散系数随温度和压力的升高而增加,扩散活化能随压力的升高而减小。研究结果为揭示CO在烟煤分子中微观吸附与扩散规律,准确预测采空区封闭火区煤自燃情况具有重要意义。     

The influence of impurities on the transportation safety of an anthropogenic CO2 pipeline

Transportation safety is a key aspect of carbon capture and storage (CCS), which is a major technology used to reduce greenhouse gas emissions. Supercritical CO₂ pipelines have been certified as an optimised choice for CO₂ transportation. The results of this study show that the Peng–Robinson (PR) equation of state is recommended for analysis of the properties of supercritical CO₂. The influence of nonpolar and polar impurities on the two-phase region and the location of the sharp discontinuity in the density are found by analysing the ternary phase equilibrium and physical parameters using the PR equation of state. A transitional area between the supercritical phase and the dense phase, where the density changes abruptly, is defined as the quasi-critical region. This study describes the functional relation between the temperature and the pressure that defines the quasi-critical line by calculating the partial derivative equations and then determines the effect of impurities on the quasi-critical region of transported CO₂. Operational recommendations for pipeline transportation of flue CO₂ are developed using a pipeline operated by Sinopec as an example, demonstrating the influence of impurities in flue CO₂ on saturation pressure for control and prevention of fractures in CO₂ pipelines.