Self-ignition of dust at reduced volume fractions of ambient oxygen

Experiments were performed to investigate the self-ignition behaviour of accumulations of four different technical dusts at oxygen volume fractions ranging from 1.3 to 21%. For this purpose a laboratory oven used for hot storage testing was modified to allow flushing with the pre-mixed oxygen/nitrogen mixture of the desired composition. It was found that for all sample volumes investigated the self-ignition temperatures were higher the lower was the oxygen volume fraction. In addition, the type of reaction changed obviously, since the apparent activation energy significantly decreased at oxygen volume fractions below 6%. However, it was still possible to observe exothermic effects at oxygen volume fractions as low as 1.3%. A numerical model was established to simulate the process of self-ignition including the coupled heat and mass transfer within the dust accumulation using a finite element solver. The model consists of six balance equations for the heat transfer and the transport of five chemical species. It shows that the model reflects self-ignition in dust accumulations with satisfying accuracy, as long as the input data generated by preceding experiments are reliable.     

A study on the influence of liquid water and water vapour on the self-ignition of lignite coal-experiments and numerical simulations

The current paper presents experimental investigations as well as numerical simulations on the influence of water and humidity on the self-ignition of combustible bulk materials.It is well known, that bulk materials may undergo self-ignition if stored under specific conditions. In some cases, large amounts of these materials are exposed to a humid surrounding, e.g. dried coal in a moist atmosphere. Due to the effects of condensation and adsorption of water, additional heat is generated and transported into the bulk material. If the pile is stored slightly below its self-ignition temperature, the bulk material can become supercritical and an ignition occurs.Experiments were carried out for German lignite coal sampled in two different particle size fractions. They showed, that subcritical deposits turned to supercritical behaviour if the relative humidity in the surrounding was suddenly increased or water was poured on the surface of the sample. Besides the experiments, a numerical model was established to describe the effects of self-heating until ignition of the deposit, including the transportation of moisture. Simulations with this model led to satisfying results when compared to the experiments.     

多元可燃气体爆炸极限理论预测模型研究

为准确掌握和预测多元可燃气体的爆炸极限,开展2种多元可燃气体爆炸极限的理论预测模型研究.第1种模型针对"多种可燃气体+多种惰性气体"在空气中或氧气中混合,基于求解可燃气体绝热火焰温度的总比热特性方法以及化学平衡反应中的贫燃料(富氧)反应,提出该多元可燃气体的爆炸下限预测模型;第2种模型针对"可燃气体+惰性气体+氧气"混...     

典型固体可燃物燃烧沉积物微观形貌特征的研究

利用火灾现场中燃烧物沉积物所特有的火灾原始信息,可以帮助火灾调查人员准确辨识与鉴别起火部位或起火点附近可燃物分部情况,辅助判断初始起火材料和起火部位的特点,通过燃烧模拟试验,开展了木材、化纤织物、棉织物、PVC制品、聚氨酯泡沫等常见固体可燃物燃烧沉积物微观形貌特征研究。首先,利用SEM 分析了不同材料沉积物中粒子分布、微观形貌等结构性差异。接着,进行了颗粒物的形貌学测量和组成成分测定。最终,得到了样本的量化差异特征。研究结果表明:5种固体可燃材料燃烧沉积物存在结构性差异,但并不显著;对组成粒子进行的形貌学测量和成分测定,可以量化区分材料属性。该方法可以为建立火灾现场起火部位可燃材料的燃烧时序性提供技术支持。     

When solids meet solids: A glimpse into dust mixture explosions

Mixing an inert solid or a less flammable compound with a combustible dust can be regarded as a direct application of the inherent safety principle of moderation. An experimental investigation was carried out to determine the evolution of the ignition sensitivity and the explosion severity of such various mixtures as a function of their compositions. It demonstrates that the introduction of small amounts of highly combustible powders (such as sulphur or nicotinic acid) to a less flammable dust (such as microcrystalline cellulose or carbon black) can strongly influence the ignition sensitivity as well as the explosion severity.It has notably been shown that the ignition sensitivity of solid/solid mixtures significantly rises up when only 10–5%wt. of highly flammable dust is introduced. Simple models can often be applied to estimate the minimum ignition energy, minimum ignition temperature and minimum explosive concentration of such mixtures. Concerning the dust explosivity, three cases have been studied: mixtures of combustibles dusts without reaction, dusts with reactions between the powders, combustible dusts with inert solid. If the evolution of the maximum explosion pressure can be estimated by using thermodynamic calculations, the maximum rate of pressure rise is more difficult to predict with simple models, and both combustion kinetics and hydrodynamics of the dust clouds should be taken into account. These results were also extended to flammable dust/solid inertant mixture. They clearly show that the concentration of solid inertant at which the ignition is not observed anymore could reach 95%wt. As a consequence, the common recommendation of solid inertant introduction up to 50–80%wt. to prevent dust explosion/ignition should be reconsidered.     

Experimental study on inert products,moisture, and particle size effect on the minimum ignition energy of combustible dusts

Handling combustible dusts not only continues to pose a risk to industry but can also affect the safety of society. Explosion risk could be avoided or mitigated trying to guarantee inherent safety throughout the product life chain. One way to reduce the risks when dealing with combustible dust is to increase the Minimum Ignition Energy (MIE) in order to decrease combustible dust ignition sensitivity. To achieve this decrease, the inertization technique, also known as moderation, will be used. It consists of adding inert powders or humidity to the combustible dust. As sometimes end-users also must deal with the handling of flammable dusts, this study aims to find the most optimal inert for toner waste from printers and Holi powder (organic coloured dust from Indian parties), taking Lycopodium as a reference. Calcium carbonate, sodium bicarbonate and gypsum are proposed as inert materials. In addition, with the aim of giving a second use to biomass boiler waste or boiler slagging, this waste will be analyzed as inert, as well as how humidity affects the combustible dusts. Then, sodium bicarbonate will be tested at different granulometries to evaluate the effect of particle size on moderation process. The tests were carried out in the modified Hartmann apparatus or MIKE 3.0. Mechanisms such as decomposition of inert dust have been analyzed by thermogravimetric analysis (TGA)). The results show that gypsum and moisture are the best performing inert followed by calcium carbonate. Boiler slagging and solid bicarbonate contribute to a decrease in the MIE in some of the tests. The reasons for this deviation are discussed in the presented article. When sodium bicarbonate is analyzed at different particle sizes, it is found that the optimum particle size does not match the particle size of the combustible dust. According to the tests, there is an optimum point for which the inert powder provides better results.     

A numerical model to simulate smouldering fires in bulk materials and dust deposits

A numerical model is presented which consists of a set of partial differential equations for the transport of heat and mass fractions of eight chemical species to describe the onset of self-ignition and the propagation of smouldering fires in deposits of bulk materials or dust accumulations. The chemical reaction sub-model includes solid fuel decomposition and the combustion of char, carbon monoxide and hydrogen.The model has been validated against lab-scale self-ignition and smouldering propagation experiments and then applied to predictions of fire scenarios in a lignite coal silo. Predicted reaction temperatures of 550 K and propagation velocities of the smouldering front of about 6 mm/h are in good agreement with experimental values derived from lab-scale experiments.     

Explosibility and thermal decomposition behavior of nitrile rubber dust in industrial processes

The formation of nitrile rubber (NBR) dust clouds during processing can lead to a potential dust explosion under certain conditions. However, the potential explosion hazard posed by NBR dust is usually overlooked by enterprises. In this paper, the explosive properties of NBR dust are investigated using a Hartmann tube, a G-G furnace, and a 20 L explosion chamber. The results showed that NBR dust could cause explosions severe enough to be classified as St-1. In addition, the thermal decomposition behavior of NBR dust under combustion conditions was investigated using a combination of thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TGA-FTIR). The results indicated that in the early stage, NBR dust mainly undergoes self-thermal decomposition to produce a large amount of combustible gas, which combines with oxygen to form a mixed gas and cause a gas-phase explosion. In addition, the participation of oxygen could lower the initial temperature of NBR dust thermal decomposition. As a result, decomposition occurred more quickly and a large amount of combustible gas was produced, thus expanding the range of dust explosions. Furthermore, these combustible gases exhibit varying degrees of toxicity, seriously affecting the life and health safety of relevant personnel. This work provides theoretical guidance for the development of safe procedures to prevent and address problems during NBR dust processing in enterprises.     

硬脂酸粉着火敏感性影响因素及惰化研究

为预防和减轻硬脂酸粉加工、储存和运输过程中的燃爆危害,采用Godbert-Greenwald恒温炉分别研究质量浓度、分散压力、惰性粉体质量分数对硬脂酸粉尘云最低着火温度的影响规律。研究结果表明：硬脂酸粉尘云的最低着火温度随质量浓度和分散压力的增加先减小后增大,当质量浓度和分散压力分别为485.4 g/m³,15 kPa时,硬脂酸粉尘云最低着火温度达到最小;添加少量惰性粉体增大了硬脂酸粉尘云分散性,对硬脂酸粉尘云最低着火温度的降低起到促进作用;随惰性粉体质量分数的增加,硬脂酸粉尘云最低着火温度先迅速增大后增速变缓;SiO₂通过物理作用抑制硬脂酸粉尘云燃烧,Al(OH)₃除物理作用外还通过化学分解参与自由基碰撞,可有效提升硬脂酸粉尘云的最低着火温度。     

Detailed analysis of flame propagation during dust explosions by UV band observations

It is important to sufficiently understand the phenomena during the dust explosions in order to take appropriate measures preventing dust explosion accidents. However, at present basic knowledge on flame propagation mechanisms during dust explosions is not enough. In this study, therefore, the flame propagation mechanisms during dust explosions are examined by detailed analyses using a special observation at UV band. Small scale experiments were performed to analyze flame propagating processes in detail. In the experiments, the stearic acid was used as the combustible particle, suspended particles were ignited by an electric spark, and flame propagation through the combustible dust was observed by using a special observation system at UV band. The leading combustion zone is observed to consist of discrete burning blue spot flames by the observation using ordinary photograph system. It is questionable how the leading flame of such discrete structure propagates. In this study, high-speed video images at UV band through a band-pass filter were taken to detect OH emission from combustion reaction zone. Using this method, the propagating flame could be detected clearly and the flame propagation mechanism could be examined in detail. In the conditions performed in this study, discrete flame propagation was not observed and the leading flame was observed to propagate continuously. This result is of importance for understanding the flame propagation phenomena during dust explosion.     

一种化学物质的热危险性研究

以某一化学物质(ANPyO)为例,探讨了化学物质热危险性分析方法和步骤:建议首先从化学结构上对物质进行初步分析,然后根据化学结构进行理论计算预测,最后在前面研究的基础上,选择和确定采用合适的,比如:DSC/TG、ARC等小药量实验方法,研究化学物质的热危险性.对于ANPyO,通过分子结构可知其为多硝基多氨基芳烃,是具有潜在的燃烧、爆炸危险的活性化学物质.理论计算预测其属于高危险性物质.对其进行DSC/TG、ARC实验,得到绝热分解反应的热力学和动力学参数,自加速分解温度( TSADT)为199℃,热分解开始温度为310.0℃,最大反应速度出现在系统温度771.5℃时,自热分解开始到最大反应速度的时间为23.5min.文中研究可为该化学物质生产、使用和储运安全提供参考.     

城市生活垃圾的热解产气特性

以城市生活垃圾中的可燃组分为实际物料,在外热式固定床热解实验台上,通过对比不同物料在不同加热温度的情况,研究了垃圾热解的产气特性,对影响产气特性的因素进行了探讨.     

Numerical investigation and theoretical prediction of self-ignition characteristics of coarse coal stockpiles

Spontaneous combustion of coarse coal stockpiles in temporary coal storage yards was investigated numerically using COMSOL Multiphysics software. The main purposes of the numerical investigation were to identify the self-ignition characteristics of coarse coal stockpiles and formulate a theoretical model to predict the self-ignition time and locations of coarse coal piles. A mathematical model for self-ignition of coarse coal piles was developed and the process of spontaneous ignition of coarse coal stockpiles was simulated. The kinetic data of low-temperature oxidation reaction was obtained from the laboratory-scale experiments with bituminous coals taken from Jindi Coal Mine of Shanxi Province in China. The influence of moisture was ignored because the studied coal had low moisture content (mass concentration: 1.87%) and both coal and ambient environment were assumed to be saturated with moisture (or ambient environment was assumed to be dry). The effects of five variables (i.e. wind velocity, oxygen concentration, height, porosity, and side slope) on the spontaneous ignition in coarse coal piles were examined. Simultaneously, a theoretical prediction model was formulated in light of variable analyses and a great number of simulations.Compared to self-ignition characteristics of fine-particle coal piles, several self-ignition characteristics of coarse coal piles were identified by numerical investigation. Wind-driven forced convection plays a predominant role in self-heating of coarse coal piles. As wind velocity increases, the self-ignition location in the pile migrates from the lower part which is close to the surface of the windward side to the upper part near to the surface of the leeward side. Wind velocity increase exerts the positive or the negative effect on self-heating, which depends on a critical wind velocity value to sustain balances of both the heat and the availability of oxygen in the coarse coal pile. The behavior of self-ignition is remarkably sensitive to both oxygen concentration and height, and a coarse coal stockpile will not ignite spontaneously as long as one of two critical variable values is satisfied: oxygen concentration of 5% or height of 3 m. The theoretical prediction model suggests when and where countermeasures should be made to prevent the self-ignition in the coal stockpile with engineering accuracy.     

数据采集在火焰闪烁频率的测量研究及分析中的应用

当可燃物燃烧时,产生的火焰通常具有一定的闪烁频率,并且每种可燃物都具有个自固定的闪烁频率,这种频率在火灾的危险度评估和火灾的监控中具有重要的研究价值.为了测量这些可燃物的火焰的闪烁频率,我们设计了数据采集系统,用多种可燃材料进行了大量的实验,研究了算法.经过处理和分析,得出了火焰闪烁频率分布在3-25Hz之间,主要频率在7-12Hz范围内,并且火焰闪烁频率与火焰大小和距红外接收器件的距离无关.基于以上结论,可以认为将火焰的闪烁频率作为判断火灾是否发生的判据是完全可以的.     

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.     

Prediction of the self-ignition temperature in lagging fires by means of isothermal calorimetry

Under certain circumstances, contamination of a porous insulation material by a combustible liquid may result in a lagging/insulation fire. In the current study, a method based on isothermal calorimetry and modelling to estimate the risk of a lagging fire, or a maximum insulation thickness for a certain system temperature, is presented. The studied system was a combination of mineral wool and rapeseed oil. Full-scale tests were performed to determine suitable ignition criteria and to validate the results from the isothermal calorimetry tests and modelling. We contaminated the lagging using two methods – a direct method and a solvent method. These methods were evaluated in the full-scale tests. The solvent method resulted in more repeatable results than the direct method, where the contaminant was poured on the insulation. Using the calorimetric measurements, we estimated the parameters for the kinetic equation. This result was used to estimate the self-ignition temperature of contaminated lagging installed on a pipe. We found that a temperature increase of 40 °C was a reasonable ignition criterion when modelling.     

The influence of initial conditions on the propagation of smouldering fires in dust accumulations

A mathematical model is presented which allows one to treat the combined phenomena of heat, mass and species transfer by diffusion as they occur within smouldering fires in accumulations of dust or other solid bulk materials. The model was applied to predict self-ignition temperatures of five different dusts, where it could be shown that computed and experimental self-ignition temperatures coincide within an error margin of ±5%.

For smouldering fires, if initiated by either self-ignition or an ignition source, it could be shown that the temperature and the velocity at which the reaction front propagates both depend on the volume of the dust accumulation. In addition, the propagation velocity increases when the initial temperature of the dust accumulation is increased and decreases when the initial moisture content of the dust accumulation is increased.

Comparisons of the numerical model with experiments show that the smouldering propagation is mirrored qualitatively, while the accuracy of the computations strongly depends on the accuracy of the input parameters, namely on the apparent activation energy.     

三元组分图在储罐退役惰性化过程设计中的应用

储罐退役之前,一般要进行惰化处理,以降低可燃气体浓度,避免形成爆炸性混合气体。根据三元组分图,可以方便、直观地设计惰化施工的方案,包括惰化操作的程序设计和危险气体控制目标浓度的确定。本文从理论上研究了在储罐退役惰性化过程设计时,如何用三元组分图表示爆炸极限、最小含氧浓度以及在储罐稀释惰性化过程中气体组成的变化轨迹。提出了两套惰化设计方案,在分析比较的基础上,确定了储罐退役惰化时的最安全实施方案。     

Hazard evaluation for chlorination and amination reactions of fluorocytosine production process

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid development of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur frequently. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study, reaction calorimeter was used to study the exothermic phenomena during the chlorination reaction and amination reaction. Differential scanning calorimetry was performed on the reactants, and thermogravimetric experiments were performed on the products. In addition, adiabatic experiment was performed to study the thermal runaway behavior of amination products under adiabatic conditions. The results showed that the target reactions generated a large amount of heat in the initial stage. The maximum temperature of amination reaction is higher than the initial decomposition temperature of the amination product under adiabatic condition. The pyrolysis of amination product was divided into three stages. The product had a high apparent activation energy at the beginning of decomposition, and the apparent activation energy decreased as the decomposition progressed.     

餐饮业烟道油垢燃烧特性及动力学模型

利用热重分析仪研究了餐饮业油烟道油垢在不同升温速率下的燃烧特性.所采用的升温速率分别为5℃/min、15℃/min和25℃/min.吹扫气体为干空气,流量为20 mL/min.结果表明,试样从常温至800℃的升温燃烧经历了第1步水分析出、第2～5步燃烧失重过程.采用Doyle和Coats-Redfern方法建立了"4阶段1级反应动力学模型",计算燃烧反应的动力学参数.并用试验热重曲线验证了模型的可靠性.研究表明,油垢燃烧失重的4个主要过程均可用简单反应动力学模型进行简化,反应级数为1;燃烧总趋势是随升温速率提高,活化能增大.