Experimental study on CO and CO2 emissions from spontaneous heating of coals at varying temperatures and O2 concentrations

Laboratory experiments were conducted to investigate carbon monoxide (CO) and carbon dioxide (CO₂) emissions from spontaneous heating of three U.S. coal samples in an isothermal oven at temperatures between 50 and 110 °C. The oxygen (O₂) concentration of an oxygen/nitrogen (N₂) mixture flowing through the coal sample was 3, 5, 10, 15, and 21%, respectively. The temperature at the center of the coal sample was continuously monitored, while the CO, CO₂, and O₂ concentrations of the exit gas were continuously measured. The results indicate that the CO and CO₂ concentrations and the CO/CO₂ ratio increased when the initial temperature was increased. As the inlet O₂ concentration increased, the CO and CO₂ concentrations increased, while the CO/CO₂ ratios tended to converge to the same value. The ratio of CO/CO₂ was found to be independent of coal properties, approaching a constant value of 0.2. The maximum CO production rate correlated well with the maximum coal temperature rise. The apparent order of reaction for coal oxidation was estimated to be between 0.52 and 0.72. The experimental results in this study could be used for early detection and evaluation of a spontaneous heating in underground coal mines.     

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.     

Law of variation for low density polyethylene dust explosion with different inert gases

To reveal the effects of different inert gases on explosion characteristics during low density polyethylene (LDPE) dust explosion and optimize the explosion-proof process, eight N₂ (CO₂)/air mixed inerting conditions were experimentally studied. Typical inerting conditions with 12 L cylindrical explosive tank were used to study the characteristics on the flame propagation. The thermogravimetric analysis with related theories were used to further explain the mechanism and quantities in low density polyethylene (LDPE) dust explosion with different inert gases. The results showed that the reduction of O₂ concentration could effectively delay the progress of flame growth process and weaken the effect of dust combustion reaction. The flame growth process of condition (N₂/air (18% O₂)) was 2.05 times slower than that of the non-inert condition. The explosion strength was obviously reduced, and the characteristic parameters such as explosion pressure and flame propagation speed were also affected by the decrease of O₂ concentration. For LDPE powder, the smaller the median diameter, the greater the explosion intensity and the lower the limiting oxygen content (LOC). The LOC with CO₂ was usually higher than that with N₂ and the effect of CO₂ was significantly better than N₂ in inerting.     

煤低温氧化热解的热分析实验研究

在热分析动力学的基础上,对阳泉煤样运用同步热分析仪进行150℃下的氧化以及热解实验,得出该煤样相应的TG-DSC曲线。通过两者的TG-DSC曲线,对比分析煤样的热量释放情况,并结合曲线设定多项式形式的机理函数以分析其动力学特性。实验研究得出:该煤的低温氧化过程较之热解过程是个明显的氧化放热过程;该煤低温氧化和热解过程的最佳机理函数都为多项式,并且相应过程中的TG曲线和DSC曲线适用于同一个机理函数,这与一般所定义的机理函数不同;热解过程较之氧化过程所需的表观活化能较大,相同条件下较易发生煤的氧化自燃。     

The effects of activated Al2O3 on the recycling of light oil from the catalytic pyrolysis of waste printed circuit boards

The effects of employing activated Al₂O₃ during the catalytic pyrolysis of waste printed circuit boards (WPCBs) are investigated, focusing on the recycling of light oil. Variations in the pyrolysis process are studied through analysis of the phase distribution, water content and boiling point fractions of the resulting products. Product composition and carbon number distribution are analyzed using gas chromatography techniques. The use of activated Al₂O₃ increases the light oil fraction and also reduces the quantity of brominated products formed. It was determined that the best yield of light oil and most efficient debromination resulted from catalytic pyrolysis at 600 °C. Applying catalyst-to-feed ratios in the range of 1.0–1.5 also maximizes the yield of light oil. The major oil fraction resulting from catalytic pyrolysis has a boiling point range of 0–250 °C and carbon number range of C6–C9, showing for use as a potential fuel after suitable treatment such as hydrogenation. At a higher catalyst-to-feed ratio of 2.0, activated Al₂O₃ generates a high proportion of light oil fractions containing a significant quantity of chemicals such as phenol (52.67% at 600 °C), although an overall lower yield of oil is obtained. The oil produced in this manner may also be used as a raw material feedstock for the production of various other useful chemicals.     

Explosion regions of 1,3-dioxolane/nitrous oxide and 1,3-dioxolane/air with different inert gases - Experimental data and numerical modelling

In this study, experimental determination and modelling investigations for the explosion regions of 1,3-dioxolane/inert gas/N₂O and 1,3-dioxolane/inert gas/air mixtures were carried out and compared. The experimental measurements were carried out at 338 K and atmospheric pressure according to EN1839 method T using the inert gases N₂, CO₂, He and Ar. The results showed that the ratio of the lower explosion limit in N₂O (LEL_N2O) to the lower explosion limit in air (LEL_air) is 0.52 and the ratio of the maximum oxygen content in air (MOC_air) to the limiting oxidizer fraction in nitrous oxide (LOF_N2O) is 0.36 ± 0.02 independent of the inert gas. When comparing the inert gas amount at the apex based on the pure oxidizing component, which is O₂ in case of air, N₂O-containing mixtures need less inert gas to reach the limiting oxidizer quantity whereas the efficiency of inert gases is in the same order. The coefficients of nitrogen equivalency however were found to differ to some extent. The explosion regions of 1,3-dioxolane/inert gas/oxidizer mixtures were modelled using the calculated adiabatic flame temperature profile (CAFTP) method as well as corrected adiabatic flame temperatures. The results indicate good agreement with experimental data for CO₂, N₂ and Ar- containing mixtures. The noticeable deviations that occur when He is the inert gas are due to the lacking transport data of that mixture.     

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.     

碱性水对煤自燃特性影响实验研究

为了研究碱性水对煤自燃特性的影响，选取葫芦素煤矿102工作面煤样作为实验煤样，利用STA-449C型同步热分析仪进行热重实验，研究加入PH=8 NaOH的煤样与原煤以及加入蒸馏水煤样在空气氛围中燃烧失重、放热量、特征温度点等变化规律，并根据Coats-Redfern积分模型计算了3种煤样燃烧反应动力学参数（活化能、指前因子）。研究结果表明:加入碱性水的2号煤样失重量较1，3号少，燃烧失重速率更低；2号煤氧化燃烧温度区间缩短，着火温度点升高，放热量少，比1，3号煤分别少485.0，480.4 J/g；3种煤样反应机理基本遵循一级化学反应函数，2号煤各段活化能高于1，3号煤，但2号煤失水活化能小于3号，表明碱性水具有抑制煤自燃效应。     

Imidazolium based ionic liquids affecting functional groups and oxidation properties of bituminous coal

Low temperature oxidation of coal will result in coal spontaneous combustion in mined-out areas. We proposed to use ionic liquids to inhibit the coal spontaneous combustion in this paper. In order to study the inhibiting effect of ionic liquid (IL) on coal oxidation, we successfully dissolved bituminous coal samples in six kinds of imidazolium based ionic liquids, [AOEmim][BF₄], [HOEmim][BF₄], [Amim][Cl], [Emim][AC], [Bmim][AC] and [Bmim][OTf]. The functional groups in the coal samples pre-treated by different ILs were detected by Fourier Transform Infrared Spectroscopy (FTIR) in detail. It is found that the ILs are capable of breaking the associated hydroxyls into dissociated hydroxyls. And during the interaction between coal and ILs, the carboxyl groups have been created. Thermo Gravimetric experiment results show that the weight loss ratios of the IL-treated coals were less during 20–400 °C stage, compared with the IL-untreated coal, which indicates that most of the easily reductive groups effectively dissolved in the ionic liquids. According to the exothermic rate curves and the computed activation energy values, it is demonstrated that the [Bmim][OTf] and [Bmim][AC] make better effect than the other ILs for depressing the oxidation rate of bituminous coal.     

煤自燃预测气体及活化能变化研究

为了研究煤在低温阶段的自燃活化能及气体产生规律,基于耗氧量与煤温间的计算模型,利用煤氧化动力学测试系统,分析了3种不同自燃性煤的低温氧化表征。结果表明:1)随着煤自燃倾向性增强,煤的耗氧量和耗氧速率逐渐增大,且其耗氧速率急剧增大的拐点温度逐渐升高;2)不同自燃性煤活化能变化规律存在显著差异,利用阶段耗氧量拐点计算出铜川和大同煤样温度分别为203℃、228℃时,活化能快速减小,开始进入自发氧化阶段;晋城煤样活化能经历先减小后增大的过程,其中过渡温度段91~135℃时,活化能最小;同时拟合出活化能(E)与指前因子(A)关系式满足动力补偿效应,验证了机理函数的合理性;3)依据复合气体CO_2/CO、CH_4/C_2H_6、C_2H_4/C_2H_6、C_3H_8/C_2H_6随温度的变化趋势,结合煤低温氧化特性,可预测煤样的氧化进程和煤体温度。     

Experimental research on inhibition performances of the sand-suspended colloid for coal spontaneous combustion

Serious mine fire disasters have occurred in Northwest China where there are abundant coal resources. For the shortage of water and loess, a large cost of conventional grouting slurry is needed. However, plenty of sand and fly ash resources have been found there. In order to improve the quality of sand injection and reduce the wastage of water during grouting, a kind of new compound material of sand-suspended colloid, which is composed of mineral inorganic gel and organic polymer, was developed in this paper. And the inhibition performance experiments of the sand-suspended colloid were carried out. The results show that the sand-suspended colloid efficaciously affected the oxidation characteristics above the critical temperature during the acceleration oxidation of the lignite and fat-gas coal samples and restrained the oxidation course by increasing the activation energy, so that it reduced the contents of CO and C₂H₄ and depressed the oxidation rate during the coal spontaneous combustion, and finally inhibited the coal spontaneous combustion.     

煤自燃特性及自然发火预测预报指标体系研究

以梁宝寺矿3号煤层为背景,采用色谱吸氧法和氧化动力法对其自燃倾向性进行了对比分析。同时,通过煤氧化升温热解实验对其升温过程中各气体随温度的变化规律进行了分析,以实验所得和灰色关联分析所得定性和定量相结合的方式,优选出了不同温度阶段煤自然发火预测预报所对应的第一、第二和第三预测指标,建立了煤自然发火预测预报体系,为有效抑制该矿及同类矿井火灾的发生具有重要意义。     

Study on the deflagration reaction process of oil gas in long-narrow confined space based on PLIF and flame spectra

Oil gas explosion in long-narrow confined space is a typical unsteady combustion process. To study the reaction process, two experiment techniques are adopted in this research. One is planner laser induced fluorescence, which is used to achieve the transient measurement of free radicals in unsteady premixed combustion field. The other one is the spectral testing technique, which is used to measure the luminescence spectrum characteristics of oil gas combustion flame. The distribution of OH radical and CH radical at different positions in the combustion field, the common partition of deflagration flame structure under different oil gas concentrations, and the main luminescence spectra of radicals such as OH, CH, C₂, C₃, CO₂, H₂O and HCO are obtained. By comparing the above three aspects, the combustion reaction process of premixed mixture is revealed, driven by the coupling effect of chemical reaction and fluid flow in the process of explosion propagation. The process can be described briefly as follows. In the “outer flame zone”, large hydrocarbon molecules are mainly transformed to small molecules and free radicals by means of pyrolysis, dehydrogenation and oxidation. In the “inner flame zone”, carbon particles and combustion products produced and gathered after relevant reactions.     

Preoptimal analysis of phase characteristic indicators in the entire process of coal spontaneous combustion

To accurately predict the development degree of coal spontaneous combustion (CSC), the CSC process was investigated using a programmed high-temperature-heating experimental system, and the variation law of index gas concentration in the holistic process of CSC and oxidation is formulated. Additionally, the accuracy of the experimental system was evaluated using experimental design for thermal analysis, and the correlation between gas index and apparent activation energy was determined using grey correlation analysis. The results indicated the following. In the critical temperature stage (0–100 °C), φ(CO)/φ(CO₂) should serve as the main index and C₂H₄ should serve as the auxiliary index; in the crack-active-speedup temperature stage (100–260 °C), CO and φ(C₂H₄)/φ(C₂H₆) should serve as the main index and R₁, the Graham index, and φ(C₂H₄)/φ(CH₄) should serve as auxiliary indexes; in the speedup-ignition temperature stage (260–370 °C), R₂ and the Graham index should serve as main indexes and φ(CO)/φ(CO₂), C₂H₄, and R₁ should serve as auxiliary indexes; in the ignition temperature (370–500 °C), R₃ should serve as the main index and R₂, the Graham index and C₂H₄ should serve as auxiliary indexes. Among them, the grey correlation degrees among the Graham index, Grignard fire coefficient, and apparent activation energy were the highest, reaching 0.91.     

Methane–air mixtures ignited by CW laser-heated targets on optical fiber tips: Comparison of targets,optical fibers,and ignition delays

Fiber optic systems are being deployed in locations where explosive gas atmospheres are normally present or are present under fault conditions. The National Institute for Occupational Safety and Health, Pittsburgh Research Laboratory (NIOSH, PRL) conducted a study of laser safety in potentially flammable environments. Researchers conducted experiments to estimate the mean and standard deviation of laser powers needed to ignite 6% methane–air atmospheres using single mode optical fiber tips covered by two types of iron oxide (Fe₃O₄ and (FeMn)₂O₃) mixed with a ceramic adhesive. The iron oxides, heated by a 1064 nm continuous wave laser, ignited the methane–air mixtures at similar powers. The minimum igniting power and maximum non-igniting power (10 tests) were 407 and 350 mW, respectively, using a 62.5 μm fiber. Laser beams guided by 125 and 80 μm diameter cladding single mode fibers produced similar methane–air igniting powers. Ignition was not observed using coal particles at powers that produced ignition with the iron oxides. Threshold ignition delays using the single mode fiber were approximately proportional to the inverse square of the igniting power. Ignition delays were significantly longer than the reported activation time for a commercial fiber optic power limiter. Comparisons are made with the results of other researchers.     

An Experimental Study on Pyrolysis of Biomass

In this study, pyrolysis of sugarcane bagasse was performed in fixed bed tubular reactor under the conditions of nitrogen atmosphere, by varying temperature and different particle sizes. The effect of final pyrolysis temperature from 400 to 500°C and the nitrogen flow rate from 50 to 200 cc min⁻¹ on the pyrolysis product yields from sugarcane bagasse have been investigated. The Maximum bio-oil yield obtained is 24.12 wt% at the final pyrolysis temperature of 450°C, N₂ flow rate of 50 cc min⁻¹ and particle size of mesh number −8 + 12. The yield of bio-oil decreases with increase in temperature from 450 to 550°C and N₂ flow rate from 50 to 200 cc min⁻¹. The various characteristics of pyrolysis oil obtained under these conditions were identified on the basis of standard test methods. The empirical formula of pyrolysis oil with a heating value of 37.01 MJ Kg⁻¹ was established as CH_1.434 O_0.555 N_0.004. The results from the pyrolysis show the potential of sugarcane bagasse as an important source of liquid hydrocarbon fuel.     

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.     

基于热爆炸理论的煤燃点确定及动力学分析

为准确判断煤燃点,提高煤自燃灾害防治能力,依据热爆炸理论,结合煤自燃过程放热曲线,将煤自燃升温过程中微分热流曲线上第1处极小值点作为煤的燃点,计算煤着火前后放热过程动力学参数变化.结果表明:随升温速率增加,煤自燃反应放热过程逐渐向高温区域移动,煤燃点逐渐增大,反应的活化能逐渐减小;同一升温速率下燃点之后煤的活化能增大;...     

Effect of Al2O3 particle size reduction on aluminium dust explosion

To investigate the effect of Al₂O₃ particle size on an aluminum explosion, the overpressure and flame velocity in a vertical duct were evaluated. The results show that the inhibitory effect of submicron Al₂O₃ is best, while the inhibitory effect increases with increasing inerting ratio. However, the inhibitory effect of micron Al₂O₃ does not increase significantly after the inerting ratio exceeds 40%. For high-concentration aluminum powder, 0.8 μm Al₂O₃ with an inerting ratio less than 20% promotes aluminum explosion. As the inerting ratio increases beyond 20%, however, the overpressure decreases. Furthermore, Al₂O₃ inhibits the formation of the intermediate product AlO and decreases the flame brightness. As the inerting ratio of 0.8 μm Al₂O₃ reaches 50%, the white patches in the flame image disappear. The results of scanning electron microscopy showed that the explosion products agglomerate and some dot-like protrusions appear on the surface of the unburned aluminum particles. The inhibition mechanism was qualitatively investigated. Physical heat absorption is proven to play a limited role. Thermal radiation and chemical inhibition play a key role. The chemical effect mainly influences the surface reaction energy source.     

A numerical modelling of an influence of CH4, N2, CO2 and steam on a laminar burning velocity of hydrogen in air

The influence of additives of various chemical natures (CH₄, N₂, CO₂, and steam) at a laminar burning velocity S_u of hydrogen in air has been studied by numerical modelling of a flat flame propagation in a gaseous mixture. It was found that the additives of methane to hydrogen–air mixtures cause as a rule monotonic reduction in the S_u value with the exception of very lean mixtures (fuel equivalence ratio ? = 0.4), for which a dependence of the laminar burning velocity on the additive's concentration has a maximum. In the case of the chemically inert additives (N₂, CO₂, H₂O) the laminar burning velocity of rich near-limit hydrogen–air flames drops monotonically with an increase in the additive's content, but no more than 1.5 times, and the adiabatic flame temperature changes slowly in this case. In the case of methane as the additive, the laminar burning velocity is diminished approximately 5 times with an increase in the adiabatic flame temperature from 1200 to 2100 K. Deviations from the known empirical rule of the approximate constancy of the laminar burning velocity for near-limit flames are shown.