多元混合气爆炸极限的非线性预测研究

根据混合气的爆炸极限与混合气各成分的体积浓度之间具有非线性关系的特点,笔者提出采用神经网络非线性方法来计算含有H2,CH4和CO的多元混合气体的爆炸极限。在模型中,H2,CH4和CO的体积浓度作为输入,爆炸上限和下限作为输出。计算结果表明,该非线性模型预测混合气爆炸下限和上限的最大相对误差为3.90%,3.57%,而模型预测值与计算值的相关系数分别为0.971,0.981;非线性模型的预测结果要好于偏最小二乘回归的预测结果。当H2,CO,CH4在混合气中的体积浓度给定时,非线性模型能够准确预测混合气的爆炸极限。     

基于绝热火焰温度混合气体爆炸下限的预测

准确地预测可燃混合气体的爆炸极限,对防止工业生产中时有发生的混合气体爆炸事故有着重大的意义。通过采用Gaseq软件计算CH4,C3H8,C2H4,C3H6,CH3OCH3和CO的绝热火焰温度(CAFT),分析初始温度对甲烷和丙烷混合气体(体积比1∶1)爆炸下限(LEL)的影响。结果表明:随着初始温度的升高,临界火焰温度基本不变,而LEL线性下降。使用计算绝热火焰温度法对不同比例的二元混合气体(体积比1∶1,3∶1,1∶3)以及三元混合气体(体积比1∶1∶1)的LEL进行预测,在选取的35组不同组份的混合气体中,LEL的预测值与文献值的平均绝对误差为0.081 8,平均相对误差为0.02。     

多元可燃性混合气体爆炸中间产物发射光谱特性实验研究

从矿井火区实际出发,选用类似于煤矿开采现场产生的多元可燃性气体:CH4,C2H6 ,C2H4,CO,H2 ,利用瞬态光谱测量系统探究了爆炸引发阶段中间产物的光谱特征,分析了组分配比、组分浓度和甲烷浓度对压力特性和中间产物光谱的影响。研究结果表明:在多组分气体加入量较小（未形成体系贫氧状态）时,3种自由基发射光谱峰值出现时间随着甲烷浓度的增大先缩短后延长;在多组分气体加入量较大（形成体系贫氧状态）时,自由基发射光谱峰值出现时间随着甲烷浓度的增大不断延长;当其以任意比例混合后,微观反应过程中关键自由基的出现顺序为:OH自由基先于O自由基, O自由基先于H自由基出现。     

煤矿其他可燃气体对空气中甲烷爆炸极限的影响

为研究矿井火区中一氧化碳(CO),氢气(H2),乙烯(C2H4)和乙烷(C2H6)等可燃气体对空气中甲烷(CH4)爆炸极限和爆炸危险度(F值)的影响及双组份可燃气体爆炸界限和爆炸危险度的变化,采用空气中可燃气体爆炸极限测定方法完成一系列试验,测定加入不同体积分数其他可燃气体时CH4的爆炸极限。其他可燃气体的加入,均使空气中CH4和混合可燃气体的爆炸界限加宽;同时加大了CH4和混合可燃气体的爆炸危险度。试验结果表明:加入C2H4气体对CH4爆炸极限影响较大,使CH4及其双组份混合气体的爆炸危险度明显增大;加入量为2.0%时,CH4的F值增加了540%。而加入CO气体比加入C2H6,C2H4和H2等气体对CH4及混合气体的爆炸极限影响都小。     

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”混合,基于热平衡方程及混合气体的各组分浓度、淬灭电势及燃烧潜热,提出该多元可燃气体的爆炸极限预测模型。结果表明:在预测多元可燃气体的爆炸极限时,第1种模型具有较广泛的应用性,且表现出较高的准确度;第2种模型具有使用简单的特点,且扩展了LCR（勒夏特列原理）的应用范围。     

受限空间内C_2H_6对瓦斯爆炸的促进机理研究

为了研究受限空间内C2H6对瓦斯爆炸的影响,采用GRI Mech 3.0甲烷燃烧反应机理对定容燃烧反应器内瓦斯爆炸过程中压力、温度变化趋势进行详细分析,同时,对瓦斯爆炸过程中关键反应步进行敏感性分析。结果表明:混合气体中依次充入0.5%、1%、1.5%、2%的C2H6,瓦斯爆炸压力、温度明显增加。其中,与混合气不含C2H6相比,加入2%的C2H6后,达到瓦斯爆炸最大压力、最高温度所对应的CH4体积分数都提前了3%,且爆炸最大压力增大了0.004MPa,爆炸最高温度升高了20K;混合气中加入C2H6,促进CH4生成反应步的敏感性系数大幅度下降,促进CO、NO生成反应步的敏感性系数升高。C2H6对瓦斯爆炸起促进作用,且随着C2H6含量的增加,瓦斯爆炸强度增大,同时,C2H6促进致灾性气体CO、NO的生成。     

受限升温煤体空间气体变化规律试验研究

为探讨升温煤体受限空间气体的变化规律,设计加工升温煤体引爆瓦斯试验平台,针对不同初始CH4体积分数开展受限空间煤体升温试验。利用Matlab计算试验数据,绘制O2,N2,CO,CH4,C2H4,C2H2的体积分数变化规律曲线。基于可燃性气体爆炸极限理论和计算公式,计算可燃性气体体积分数与混合气的爆炸上下限值,并绘制其关系图。结果显示,当温度为190~400℃时,受限空间气体将失去爆炸性。分析现场煤自燃引爆瓦斯的条件和形式,提出防治煤自燃引爆瓦斯的重点是防止煤柱、断层和高冒煤自燃升温到更高温度,尤其是要防止该区域提前氧化升温,同时要保持工作面风流稳定。     

针对C3H8／空气扩散火焰的PCA简化机理构筑

C3H8是液化石油气（LPG）的主要成分,其火焰结构的数值预测对于消防等相关行业具有重要意义。单步或总包反应过于简单,不能描述碳氢燃料的氧化机制,而耦合燃料详细机理的燃烧模拟计算量大,且描述反应的数学系统具有极强的“刚性”,限制了反应机理的实际应用,而去除冗余反应和组分的简化机理具有描述燃烧的全面性优点,且降低了数学系统的“刚性”,因此耦合简化机理的火焰结构数值预测具有优势。本文采用基于矩阵分析的主成分（PCA）分析技术,分析研究了wang等发展的469步C3H8详细反应动力学机理,获得了组分的重要性排序,基于此分别构筑了320步和214步两个简化机理,针对典型扩散火焰的计算,表明建立的两个简化机理具有较高的模拟可靠性,同时也提供了一种框架简化机理的构筑方法。     

航空压力环境对锂离子电池热解气体爆炸极限影响*

针对航空锂离子电池热失控释放气体安全性研究不足的问题,采用气体拉曼光谱技术、气相色谱仪(Gas Chromatography,GC)和质谱(Mass Spectroscopy,MS)耦合来探究压力和荷电状态(State of Charge,SOC)对锂离子电池早期故障气体类型、气体动态演变及气体潜在危险性等特征的影响规律,同时综合考虑压力、电压和电池温度等多种因素分析锂离子电池热失控危害。研究结果表明:电池SOC越高且环境压力越低,电池越早触发热失控,爆炸极限越宽,其中30 kPa下100%SOC电池热解气体爆炸极限为8.01%~53.35%;SOC和环境压力越高,电池热失控越危险,释放的气体体积越多;CO,CO2,PF3,C2H4及电解液（C3H6O2、C3H6O3、C4H8O2）等气体可作为航空锂离子电池早期故障诊断特征。研究结果对保障锂离子电池在航空领域的安全运输及应用具有重要意义。     

基于分段拟合的煤自燃指标气体优选研究*

为更加精确地得出煤自燃的临界温度并找出煤自燃各个阶段最优的指标气体,以此提高煤层自燃预测预报的准确性,选取西北某矿2号煤和3号煤典型煤样开展程序升温-气相色谱实验,采用分段直线拟合的方法,得出煤自燃过程中的耗氧速率突变点温度和氧化产物生成量激增点温度,在此基础上采用灰色关联度分析法对煤干裂温度之后的指标气体进行优选。结果表明:2号煤和3号煤的自燃临界温度分别为73.0 ℃和72.1 ℃,干裂温度分别为112.6 ℃和109.8 ℃;CO适用于2种煤样全温度下的预测预报;φ(C2H4)/φ(C2H6)和C2H4是2号煤干裂温度之后较优的预测预报指标气体;φ(C2H4)/φ(C2H6),C2H4和C2H6是3号煤干裂温度之后较优的预测预报指标气体。     

Development of machine learning based prediction models for hazardous properties of chemical mixtures

Lower flammability limit (LFL), upper flammability limit (UFL), auto-ignition temperature (AIT) and flash point (FP) are crucial hazardous properties for fire and explosion hazards assessment and consequence analysis. In this study, a comprehensive prediction model set was constructed by using expanded chemical mixture databases of chemical mixture hazardous properties. Machine learning based gradient boosting quantitative structure-property relationship (GB-QSPR) method is implemented for the first time to improve the model performance and prediction accuracy. The result shows that all developed models have significantly higher accuracy than other regular QSPR models, with the 5-fold cross-validation RMSE of LFL, UFL, AIT, and FP models being 1.06, 1.14, 1.08, and 1.17, respectively. All developed QSPR models can be used to estimate reliable chemical mixture hazardous properties and provide useful guidance in chemical mixture hazard assessment and consequence analysis.     

初始温度对可燃气体爆炸下限影响的研究

研究初始温度对可燃气体爆炸下限的影响规律,运用阿累尼乌斯定律,可得出温度与化学反应速度之间的关系式,从而得出简化的温度和爆炸极限影响的模型。利用该模型对5种烷烃在不同温度下的爆炸下限实验值进行拟合相关度比较,所得爆炸下限模型平均拟合相关系数达到0.995 5。结果表明,该简化模型具有较强的可靠性。     

A correlation of the lower flammability limit for hybrid mixtures

Hybrid mixtures are widely encountered in industries such as coal mines, paint factories, pharmaceutical industries, or grain elevators. Hybrid mixtures explosions involving dust and gas can cause great loss of lives and properties. The lower flammability limit (LFL) is a critical parameter when conducting a hazard assessment or developing mitigation methods for processes involving hybrid mixtures. Unlike unitary dust or gas explosions, which have been widely studied in past decades, only minimal research focuses on hybrid mixtures, and data concerning hybrid mixtures can rarely be found. Although methods to predict the LFL have been developed by using either Le Chatelier's Law, which was initially proposed for homogeneous gas mixtures, or the Bartknecht curve, which was adopted for only certain hybrid mixtures, significant deviations still remain. A more accurate correlation to predict an LFL for a hybrid mixtures explosion is necessary for risk assessment. This work focuses on the study of hybrid mixtures explosions in a 36 L dust explosion apparatus including mixtures of methane/niacin, methane/cornstarch, ethane/niacin and ethylene/niacin in air. By utilizing basic characteristics of unitary dust or gas explosions, a new formula is proposed to improve the prediction of the LFL of the mixture. The new formula is consistent with Le Chatelier's Law.     

Influence of concentration distribution of hydrogen in air on measured flammability limits

There is a clear difference between exiting data on the measured flammability limits of hydrogen-air mixture. The non-uniformity of concentration distribution of hydrogen in air is a contributor to deviations of the upper flammability limit (UFL) and the lower flammability limit (LFL) measured in different experiments. This paper presents a numerical model to simulate the gas mixing process from start to stability, to predict the concentration distribution, and to research the influence of concentration distribution of hydrogen in air on measured UFLs and LFLs. The commercial software package Fluent was used to carry out the numerical simulation for the concentration distribution of hydrogen in air in the vessels with length-to-diameter ratios (L: D) of 1:1, 3:1, 5:1 and 7:1 respectively. Based on the numerical simulation and analysis, the influence of concentration distribution on measured flammability limits was demonstrated for hydrogen in air in the vessel. It is found that the deviations of measured flammability limits of hydrogen in air are the minimum in the vessel with length-to-diameter ratio of 1:1, and augment with the augmentation of vessel length-to-diameter ratio. Moreover, it is presented that the deviations of measured flammability limits of hydrogen in the center of the vessel are lower than that in the top and the bottom.     

腐朽坑木与煤混合物升温氧化特性研究*

为研究煤层及腐朽坑木着火特性,采集巷道内腐朽坑木与煤样并进行混合,对其混合物进行燃点测定和程序升温实验;通过对不同煤木混合物在升温过程中产生气体的规律性进行分析,优选出混合物产生的单一气体指标及复合指标。研究结果表明:随朽木在混合物中的比例上升,混合物燃点呈下降趋势,且CO,C2H4等指标气体出现更早,CO产生量更大;腐朽坑木达到燃点后会发生阴燃并逐渐升温引燃煤炭,加速煤氧化进程,最终导致火灾的发生;CO,CO/CO2比值、ICO指标可作为本煤层着火主要预测指标气体及指标,C2H4,C2H6可作为辅助指标气体;该方法可准确判定煤火灾发生发展程度,对实际生产具有理论指导意义。     

Effects of N2 and CO2 on the flammability of 2,3,3,3-tetrafluoropropene at elevated temperatures

The flammability characteristics of refrigerants are affected by environmental factors, making them prone to flammability and explosion accidents in cooling systems. In this paper, the flammability characteristics of R1234yf–air mixtures with N₂ and CO₂ were investigated comparatively at temperatures between 20 and 50 °C at 80% relative humidity. The lower and upper flammability limits of R1234yf were measured. The limiting oxygen concentration (LOC), critical flammable ratio (CFR), and critical flammable concentration (CFC) of the R1234yf–air mixtures with inert gases were investigated. The paper developed a linear formula between the flammability limit of R1234yf and the temperature. The changes in CFC with different temperatures were negligible for R1234yf. Furthermore, the mixed refrigerant had both non-flammability and the lowest vapor pressure when the CFR of the R1234yf/CO₂ mixture was 2.9. The experimental results were used to propose a new prediction model to estimate the flammability limits of R1234yf. Finally, molecular simulation explained the effect of inert gases on the flammability of R1234yf from a microscopic point of view. The research aimed to provide valid evidence and data for preventing flammable and explosive refrigerant incidents.     

Prediction of flammability limits of fuel-air and fuel-air-inert mixtures from explosivity parameters in closed vessels

Flammability limits of fuel-air and fuel-air-inert gaseous mixtures, especially at non-atmospheric conditions, are essential properties required for establishing safety operating conditions for handling and processing flammable gases. For pure fuels, an important data pool exists, formed by the flammability limits of fuel-air and fuel-air-inert gaseous mixtures at ambient initial conditions measured by standard methods. Such methods can be used for experimental determination of flammability limits for multi-fuels mixed with air, with or without additives, under non-atmospheric conditions. Their use is however a time- and material-consuming process; in addition, the flammability limits obtained by various standard methods may be scattered as a result of different choices in the operating parameters, for each standard method. It appears that a preliminary estimation of the flammability limits for fuel-air and fuel-air-inert gaseous mixtures can minimize the effort of measuring them in specific initial conditions.The present paper describes a new method for estimating the flammability range of fuel-oxidizer gaseous mixtures based on measurements of explosivity properties e.g. the peak explosion pressure and maximum rate of pressure rise recorded during closed vessel laminar explosions of fuel-oxidizer mixtures far from limits. Data obtained for several hydrocarbon-air gaseous mixtures with or without inert gas addition are used to examine the accuracy of estimated flammability limits (LFL – the lower and UFL – the upper flammability limit) as well as of the Limiting Oxygen Concentration (LOC) and the Minimum Inert Concentration (MIC). The predictive ability of the proposed method is examined against the predictive ability of other recently described methods.