High temperature oxidation of inoculated high Si/SiMo ductile cast irons in air and combustion atmospheres

The present work aims to investigate the effect of heating temperature(400,600 and 800°C)and inoculating elements(Ca,Ca-Ba,Ca-RE)on oxidation behavior of ductile irons containing 5.25%Si and 4.8%Si-2.3%Mo in dry air and combustion gas containing water vapour(natural gas burning).The oxidation is influenced by the gas atmosphere type,the iron alloying system,and the inoculating elements depending on the heating temperature.The weight gain increases from 0.001%-0.1%(400°C)to 0.05%-0.70%(600°C)and up to 0.10%-2.15%(800°C).No particular effects of the considered influencing factors are found when heating at 400°C,while at 600°C,mainly the oxidation gas atmosphere type shows a visible influence.At the highest heating temperature of 800°C,a limited increase of the weight gain is found for dry air atmosphere(up to 0.25%),but it drastically increases for combustion atmospheres(0.65%-2.15%).The water vapour presence in the combustion atmosphere is an important oxidising factor at 600-800°C.The alloying system appears to influence the oxidation behavior mainly at a heating temperature of 800°C in the combustion atmosphere,as evidenced by the lower weight gain in 5.25%silicon cast iron.Positive effects of inoculating elements increase with the heating temperature,with Ca and Ba-FeSi inoculation generally showing better performance.Irons inoculated with CaRE-FeSi exhibit a higher degree of oxidation.These results are in good relationship with the previous reported data:Ca-Ba-inoculation system appears to be better than simple Ca for improving the graphite parameters,while RE-bearing inoculant negatively affects the compactness degree of graphite particles in high-Si ductile irons.As the lower compactness degree is typical for graphite nodules in high-Si ductile irons,which negatively affects the oxidation resistance,it is necessary to employ specific metallurgical treatments to improve nodule quality.Inoculation,in particular,is a potential method to achieve this improvement.

Bifurcation characteristics of coal spontaneous combustion and analysis of critical state of gaseous reaction in a packed bed

The numerical model was presented for the coal combustion in the packed bed. The bifurcation characteristic of the ignition-extinction of solid-phase smoldering and tran- sition to flaming was studied for the packed bed of coal.One of the Frank-Kamenetskii parameter β_1 was selected as the control parameter.The computed results show that the bifurcation curve is obviously divided into two zones of solid-phase reaction and gas- phase reaction,and the total process of ignition-extinction presents twice bifurcation cha- racteristic.Moreover,the vanishing of critical state of ignition-extinction is studied.One of the transition points,ε_2=0.05,is numerically solved for the vanishing of critical state.The larger the value of ε_2 is,the easier the gas-phase can react.However,the combustion temperature will decrease with increasing ε_2.The other transition point α_2=0.53 is also ob- tained.With increasing the value of α_2,the combustion temperature of gas-phase reaction is close to the smoldering temperature of coal.When α_2 is infinite,the only reaction occur- ring is the smoldering combustion of solid-phase,and the gas-phase cannot react.

Risk assessment of gas control and spontaneous combustion of coal under gas drainage of an upper tunnel

The adjustment of the gas drainage rate has an immediate impact on air leakage in gob,thus resulting in the change of self-heating of coal.While regulating the gas drainage parameters,the risk of spontaneous combustion of coal should be considered.The risk assessment of gas control and spontaneous combustion of coal under gas drainage in a tunnel was investigated at different gas drainage rates.The distributions of the air volume along the working face,the gas management effects and the width of the oxidation zone were subjected to risk analysis.As the simulation results showed,with increasing gas drainage rate,although the safety of gas dilution by ventilation was assured,the intensifying air leakage caused the oxidation zone to move into the deeper gob and led to an increase in the width of the oxidation zone.A risk assessment method was proposed to determine a suitable gas drainage rate for the upper tunnel.The correctness of the risk assessment and the validity of the numerical modelling were confirmed by the field measurements.

Characteristics of coal re-oxidation based on microstructural and spectral observation

In order to investigate the characteristics of re-oxidation of residual coal in goafs in close coal seam mining,scanning electron microscope and infrared spectrometer are used to study the changes of coal microstructure and chemical reaction of functional groups of eight coal samples at different ranks.Result shows that after initial oxidation,the surface morphology of pore are different,and the porosity of coal is increased and the oxygen adsorption capacity of coal is improved.The change of coal molecular structure and presence of a large amount of active oxygen-containing functional groups lead to increasing tendency of coal to further oxidation.In addition,the higher lever of the initial oxidation is,the easier the re-oxidation occurs.

Effects of pyrite on the spontaneous combustion of coal

Abstract Pyrite has a significant effect on the spontaneous combustion of coal. The presence of pyrite can change the propensity of coal towards spontaneous combustion. The influences of various pyrite contents on the parameters of spontaneous combustion, such as index gases, temperature and released heat etc., were investigated in this study, Coal samples with different pyrite contents （0 %, 3 %, 5 %, 7 % and 9 %） were made by mixing coal and pyrite. The oxidation experiments under temperature-programmed condition were carried out to test the release rate of gaseous oxidation products at different temperatures. Differential scanning calorimeter （DSC） was employed to measure the intensity of heat release during coal oxidation for various pyrite contents. The results indicate that pyrite can nonlinearly accelerate the process of spontaneous combustion. The coal sample with a pyrite content of 5 % has the largest CO release rate and oxygen adsorption as well. However, the coal sample with a pyrite content of ？ % has the largest rate of heat flow according to the results from the DSC tests. Pyrite contents of 5 %-7 % in coal has the most significant effects on spontaneous combustion within the range of this study. The conclusions are conducive to the evaluation and control for the spontaneous combustion of coal.

The shortest period of coal spontaneous combustion on the basis of oxidative heat release intensity

It’s necessary to forecast the shortest spontaneous combustion period for preventing and controlling the coal spontaneous combustion.During the experimental process,a calculating model of the SSCP is established on the basis of the oxidative heat release intensity and thermal capacity at different temperatures.According to the basic parameters of spontaneous combustion,heat of water evaporation and gas desorption,the SSCPs of different coals are further predicted.Finally,this study analyzed the relationships of the SSCP and the judging indexes of the self-ignite tendency.The result shows that the SSCP non-linearly increases with the decrease of dynamic oxygen adsorption and increase of activation energy.Compared with the practical fire situation of mine,this reliable method can meet the actual requirement of mine production.

Comparative study on the flame retardancy of CO_(2) and N_(2) during coal adiabatic oxidation process

To test the effectiveness of N_(2) and CO_(2) in preventing coal from spontaneously combusting,researchers used an adiabatic oxidation apparatus to conduct an experiment with different temperature starting points.Non-adsorbed helium(He)was used as a reference gas,and coal and oxygen concentration temperature variations were analyzed after inerting.The results showed that He had the best cooling effect,N_(2) was second,and CO_(2) was the worst.At 70℃and 110℃,the impact of different gases on reducing oxygen concentration and the cooling effect was the same.However,at the starting temperature of 150℃,CO_(2) was less effective in lowering oxygen concentration at the later stage than He and N_(2).N_(2) and CO_(2) can prolong the flame retardation time of inert gas and reduce oxygen displacement with an initial temperature increase.When the starting temperature is the same,N_(2) injection cools coal samples and replaces oxygen more effectively than CO_(2) injection.The flame retardancy of inert gas is the combined result of the cooling effect of inert gas and the replacement of oxygen.These findings are essential for using inert flame retardant technology in the goaf.

Changes in active functional groups during low-temperature oxidation of coal

Using Fourier Transform Infrared (FTIR) combined with an adiabatic oxidation test, temperature-programmed oxidation and gas analysis, we studied the changes of active functional groups during low-temperature oxidation of lignite, gas coal, fat coal and anthracite. During slow low-temperature heat accumulation, aliphatic hydrocarbons, such as methyl and methylene, are attacked by oxygen atoms absorbed by pores on coal surfaces, generating unstable solid intermediate carbon-oxygen complexes, which then decompose into gaseous products (CO, CO2) and stable solid complexes. At the accelerated oxidation stage, the stable complexes begin to decompose in large amounts and provided new active sites for further oxidation, while the aliphatic structures gained energy and fell from the benzene rings to produce CxHy and H2.

Experimental study on the oxidation kinetics of coal in typical coal mining areas of the Southern Junggar coalfield,Xinjiang,China

Coal spontaneous combustion(CSC)is a disaster associated with coal mining that leads to loss of coal resources and envi-ronmental and human health issues.To investigate kinetic characteristics for oxidation of coal,three coal samples were collected from different coal mining areas in the Southern Junggar coalfield.Subsequently,the collected coal samples were ground into different particle sizes and tested using microscopic and macroscopic methods,including thermal gravimetric analysis,Fourier transform infrared spectroscopy,X-ray diffraction,and temperature-programmed oxidation.The results obtained are as follows:the sharpest absorption peak(002)indicates that graphitization is high.Furthermore,the results show that the SKS coal sample is prone to spontaneous combustion;the greater the aromatic hydrocarbon content is,the more difficult it is for CSC to occur,while the opposite is true for oxygen-containing functional groups.The SKS data confirmed this conclusion;the rate for generation of CO and CO_(2)controlled the possibility of SKS oxidation at 110℃and provided an indication of the temperature.During the dehydration stage,the WD sample had the lowest activation energy,indicating that it was most susceptible to spontaneous combustion.During the combustion stage,the lowest activation energy was found for the SKS sample with particle sizes<0.075 mm,indicating that particle size was one of the factors affecting spontane-ous combustion.The activation energy for dehydration was significantly lower than that for combustion,which showed that the coal oxygen reaction was more likely to occur in the dehydration stage.Based on DSC curves,the SKS sample had the largest exothermicity,indicating that it would ignite more readily.

Correlations among factors of sulfide ores in oxidation process at ambient temperature

Spontaneous combustion is one of the serious problems in the mining of sulfide ore deposits. The relevant factors, e.g. oxygen absorption quantity, mass increase, contents of water soluble iron ions and sulfate ion of sulfide ore samples in the oxidation process were investigated both in theory and experiment. The results from the investigation show that there is no general interpretation relation among the oxygen absorption quantity, the contents of sulfate ion and water soluble iron ions during the oxidation process of sulfide ores at ambient temperature. However, there is a linear relationship between the mass increase of the sulfide ore samples in the oxidation process at ambient temperature and the quantity of oxygen absorption. Therefore, the simple and cheap mass scaling method is suitable for predicting the oxygen absorption performance of sulfide ores at ambient temperature in place of the expensive and complicated chemical method used hitherto. Furthermore, combined with other items of breeding fire test, the mass increase potential can also be used to predict the spontaneous combustion tendency of sulfide ores.

Test of oxidation behavior of sulfide ores at ambient temperature for fire control

The coincidence of relevant factors, e.g. oxygen absorption quantity, weight increment, water soluble iron ions and sulfate ion of sulfide ore samples in the oxidation process, was tested through experiment. Based on a large number of tests for a group sample of sulfide ores from a mine, some important conclusions were obtained. The results obtained by the investigation indicate that there is no general interpretation relative to the oxygen absorption and the formation products of sulfate ion and water soluble iron ions during the oxidation process of sulfide ores at ambient temperature. However, the weight increment of the sulfide ore samples in the oxidation process at ambient temperature has a linear relationship with the auantitv of oxvaen absorption.

An analytical model to estimate the time delay to reach spontaneous ignition considering heat loss in oil reservoirs

During air injection into an oil reservoir,an oxidation reaction generates some heat to raise the reservoir temperature.When the reservoir temperature reaches an ignition temperature,spontaneous ignition occurs.There is a time delay from the injection to ignition.There are mixed results regarding the feasibility of spontaneous ignition in real-field projects and in laboratory experiments.No analytical model is available in the literature to estimate the oxidation time required to reach spontaneous ignition with heat loss.This paper discusses the feasibility of spontaneous ignition from theoretical points and experimental and field project observations.An analytical model considering heat loss is proposed.Analytical models with and without heat loss investigate the factors that affect spontaneous ignition.Based on the discussion and investigations,we find that it is more difficult for spontaneous ignition to occur in laboratory experiments than in oil reservoirs;spontaneous ignition is strongly affected by the initial reservoir temperature,oil activity,and heat loss;spontaneous ignition is only possible when the initial reservoir temperature is high,the oil oxidation rate is high,and the heat loss is low.

Analysis on the Governing Reactions in Coal Oxidation at Temperatures up to 400&deg;C

The present study aims to further understanding of the principal reactions that occur during coal oxidation at moderate temperatures. Mass change and heat evolution of a sample were monitored by thermo-gravimetric analysis coupled with differential thermal analysis (TGA/DTA). Gaseous and solid products were traced using online or in situ Fourier trans- form infrared spectroscopy (FTIR). Measurements were conducted by heating the samples up to 400?C, with the O2 concentration in the reaction medium set at 0, 10, 21, and 40 vol%, respectively. It was observed that the mass increase of a sample between 150?C and ~275oC was a result of the accumulation of C=O containing species in the coal structure, whereas substantial mass loss and heat evolution of a sample at ~400oC can be attributed to the significant involvement of the direct “burn-off” reaction. Enrichment of O2 inthe reaction medium leads to the acceleration in oxygen chemi- sorption, formation and decomposition of the solid oxygenated complexes, as well as the “burn-off” reaction. With the temperature increasing, the oxidation process governed by oxygen chemisorption gradually shifts to that by significant decomposition reactions, and eventually to that by the direct “burn-off” reaction. Temperature boundaries of these stages can be determined using parameters defined based on a set of TG/DTA data. Shift in the governing reactions is essentially due to the diverse requirements of reactants of the reactions and their energy barriers to be overcome. In en- gineering practice, the phenomena of self-heating and spontaneous combustion of coal correspond to chemisorption and the direct “burn-off” reaction, respectively.

Investigation into the surface active groups of coal

The oxidation heat of coal is the direct reason leading to coal spontaneous combustion. When coal is exposed in oxygen atmosphere, the physical adsorption and chemisorption happened, and then which resulting chemical reaction followed heat between coal and oxygen. Owing to the complexity and uncertain of molecular structure of coal,it was only reduced that bridge bonds, side chains and O 2 containing functional groups in coal may be prone to oxidation in last year, but not to deeply investigate into the structures and the type of the active radicals. In this paper, according to the last achievements in coal structure research, the hypomethylether bond, hypoalkyl bond of α carbon atom with hydroxyl and α carbon atom with hypomethy side chain and hypomethyl bonds linking up two aromatic hydrocarbon in bridge bonds, and methoxy,aldehyde and alkyls of α carbon atom with hydroxy in side bonds are inferred to be free radical easily to lead to oxidize coal under the ambient temperature and pressure. The order from strong to weak of oxide activation of the seven surface active groups is aldehyde side chains, hypomethylether bonds, hypoalkyl bonds of α carbon atom with hydroxyl, hypoalkyl bonds of α carbon atom with hypomethyl, hypomethyl bonds linking up two aromatic hydrocarbon,methoxy, alkyls side chains of α carbon atom with hydroxyl. Because of the two unsaturated molecular tracks of O 2, unpaired electron clouds of the part of surface active groups of coal enter molecular tracks of O 2 to lead to chemisorb on the conjugate effect and induced effect of surface active groups, and then chemical reaction followed heat happens in them. On the basis of change of bond energy, weighted average method is adopted to count the reaction heat value of each mol CO,CO 2 and H 2O. The property of coal spontaneous combustion is different for the different number and oxidability of the active structure in the coal resulting in the different oxidation heat.

深部开采高温热液侵蚀煤自燃特性

深部开采过程中,矿井水温度显著高于浅部煤层,高温热液侵蚀作用影响着煤体物化特征,进而对其自然发火特性产生影响。为研究深部开采热液侵蚀作用下的煤自然发火特性及其影响机制,通过低场核磁共振、分子动力学模拟、力学测试及C600微量热实验,分析了热液侵蚀作用对煤体孔隙度、孔径分布、力学强度、氧化热特征参数的影响规律,并结合相关性分析,定量描述了各个参数间的相关度。研究结果表明:热液侵蚀煤体受热应力和溶胀作用的双重影响,内部孔隙结构发生显著变化,热液温度与煤体总孔隙度之间存在显著正相关关系,相关系数为0.97;随着热液温度的升高,煤体总孔隙度由0.24%增长至1.35%,微孔占比由69%以上降至60%以下,中孔、大孔占比增大;煤体孔隙大小显著影响着氧气的扩散系数,随着煤体孔隙宽度的线性增加,氧气扩散系数呈指数增加;受高温热液侵蚀作用影响,煤体孔隙发育以及部分有机质的溶解显著降低了煤体的力学强度,从原煤到80℃热液侵蚀煤体,其抗压强度均值由23 MPa降低至11.6 MPa,降低了50%;相较于原煤,热液侵蚀煤体的放热强度更高,放热量更大,TH40、TH50、TH60、TH70、TH80放热量分别增加了12.61%、16.63%、17.32%、19.36%和25.02%,热液温度与煤氧化放热量间相关系数为0.92。高温热液侵蚀作用显著影响着煤的孔隙度及氧化过程,随着热液温度升高,煤体孔隙度增大,力学强度减弱,氧化过程耗氧量及氧化速率加快,放热量增加。高温热液侵蚀煤具有更高的自燃危险性,且热液温度越高,风险越大。

混合气体抑制煤自燃的实验研究

为了研究混合气体(O_(2)/N_(2)和O_(2)/N_(2)/CO_(2))对煤自燃特性的影响,利用同步热分析仪、程序升温-气相色谱联用仪/红外光谱仪研究煤在混合气体下的特征温度、热效应/标志气体及官能团变化。结果表明:O_(2)/N_(2)气体氛围(简称气氛)下,随着N_(2)体积分数的增加,特征温度点滞后,TG、DTG、DSC均向高温偏移,放热量减少,燃烧阶段活化能升高,煤的最终耗氧量和CO体积分数均降低,煤中羟基增加,脂肪烃、含氧官能团、芳香烃的含量呈减少趋势;O_(2)/N_(2)/CO_(2)气氛下,随着CO_(2)体积分数的增加,特征温度点后移,放热量下降,燃烧阶段活化能减小,耗氧量、CO体积分数均降低,羟基、脂肪烃增加,含氧官能团的含量减少;当O_(2)体积分数相同时,O_(2)/N_(2)/CO_(2)混合气体中的失重率峰值、耗氧量与CO体积分数均小于O_(2)/N_(2)混合气体;-OH易被氧化发生脱水反应,煤在反应初期放热量较少,后期放热量快速增加,CO主要由-C=O生成。

岩块尺度对采空区煤自燃区域的影响研究

为探究综放采空区岩块尺度对煤自然发火的影响,采用Fluent软件数值模拟不同直径岩块条件下采空区的煤自燃规律,分析采空区氧浓度场和风速场,分别以氧气体积分数和风速为指标,确定采空区氧化带面积并以二场叠加场作为采空区煤自燃危险区划分标准,研究煤自燃危险区域与岩块直径的关系。研究结果表明:当岩块直径由0增加到10 m时,以氧气体积分数为指标,氧化带宽度变小,面积由5563.84 m^(2)减至2602.69 m^(2);以风速为指标,氧化带面积由3376.60 m^(2)减至1262.95 m^(2);将2种指标确定的氧化带进行叠加得到煤自燃危险区,随着岩块直径的增加,其面积由1854.04 m^(2)减至552.91 m^(2),煤自燃危险区最大宽度由20.40 m缩减至9.06 m。研究结果可为采空区煤自燃发火区域的确定提供参考。

孟巴矿高地温环境煤孔隙及氧化动力学特征

为预防高地温煤层开采条件下煤自燃灾害,明确煤的自燃特性,以孟巴矿Ⅵ煤层1306工作面煤样为例,将煤样分别置于40、50、60℃控温炉中恒温处理30天,采用全自动比表面积和孔径分布分析仪测试煤的孔隙结构,利用同步热分析仪测试原煤样和高温预处理煤样的氧化动力学参数。结果表明:孟巴矿煤样经高地温作用后,煤的小孔比例减小,中孔和大孔比例增大,煤样经60℃处理后比表面积由原煤的2.351 m^(2)/g增至3.285 m^(2)/g,总孔容由原煤的0.00788 mL/g增至0.01001 mL/g;与原煤相比,高地温处理后煤样点火温度和燃尽温度显著降低,最大失重量、最大失重速率分别提高6.1%和23.3%;高温处理后煤样的活化能和指前因子均小于原煤,说明高地温环境显著提高孟巴矿煤样的氧化反应活性,增大煤自燃的危险性。

淮南矿区典型煤样自燃特性热重-红外联用实验研究

为降低煤矿安全事故发生风险,针对煤自燃氧化出现紧急危险性等问题,研究淮南矿区典型煤样的自燃特性。以淮南张集煤矿6、8、11-2和13-1煤样为例,通过热重-红外(TG-FTIR)联用技术分析煤样在升温氧化过程中的质量变化和气相产物析出特性。实验结果表明:四种煤样的升温氧化过程均可分为5个阶段,包含6个特征温度点;燃烧阶段各煤样反应活化能按由大到小排序为6煤、8煤、11-2煤、13-1煤;主要气相产物吸收峰强度按由高到低排序为13-1煤、11-2煤、8煤、6煤;根据活化能大小和主要气相产物吸收峰强度判断各煤样自燃风险按由高到低排序为13-1煤、11-2煤、8煤、6煤。本文结果可为类似矿区矿井火灾防治提供基础理论支撑。

采空区复合灾害环境下含瓦斯煤自燃特征研究进展

采空区瓦斯与煤自燃复合灾害日趋成为制约矿井安全生产的主要灾害模式,煤自燃作为瓦斯燃烧、爆炸等灾害事故的“点火源”,无疑是防范煤矿采空区复合灾害的关键。目前关于采空区遗煤残余瓦斯(吸附态为主)与风流瓦斯(游离态)对煤自燃影响机理的认识还不够深入,为此探究了含瓦斯条件下煤自燃相关研究的最新进展。现阶段针对含瓦斯风流/气氛下煤自燃特性的研究内容较为丰富,但吸附态瓦斯影响条件下的煤自燃特性实验平台及相关研究成果较匮乏。研究表明,游离瓦斯易引起煤低温氧化气体产物出现明显的“滞后效应”,同时煤体放热强度减弱、活化能整体增大,这反映出氧化气氛中的瓦斯对煤自燃具有抑制作用;相应地,煤自燃过程中的官能团、自由基及煤微晶结构等微观特征参数均会随瓦斯体积分数呈现规律性演变。进一步,考虑到遗煤内部残余瓦斯与风流瓦斯的赋存状态差异,探究了瓦斯对煤自燃过程的影响机理,包括CH4对O_(2)的驱替稀释作用、CH_(4)与O_(2)的竞争吸附解吸引起的置换效应,以及高温环境下的O_(2)分子化学吸附和煤氧复合效应作用。基于此,提出了采空区遗煤在吸附态瓦斯影响下的自燃过程特性、含瓦斯煤自燃流–固–热–化多场耦合特征、含瓦斯煤自燃监测预警理论应用等亟待突破的瓶颈问题。