Lower flammability limits of flammable ternary organic mixtures: Synergistic behavior

Organic flammable liquids and their mixtures, which possess high risk of combustion and explosion, are widely used as raw materials and solvents in chemical and pharmaceutical industries. Lower flammability limits (LFL) is one of the most important parameters to characterize the combustion and explosion hazards of combustible gases and liquid vapors. The LFL of various ternary organic mixtures consist of ketone (acetone and butanone), ester (ethyl acetate) and alcohol (ethanol and isopropanol) were tested at 25 °C and atmospheric pressure. The results showed that resulted LFL values of the experiment were always lower than those calculated by volume fraction weighting method when the volume fraction of alcohol was less than 20 vol% but more than 10 vol%. The co-existence of alcohol and ethyl acetate had synergistic effect on reducing the LFL values of ternary organic mixtures and thus increased their explosive risk. The mechanism of synergistic effect was analyzed, and the results showed that the OH· and H· radicals produced by the oxidation decomposition of alcohols and esters accelerated the oxidation process of ternary organic mixtures, which led to the decrease of experimental LFL values and thus corresponding increased of their explosive risk. This study would be expected to provide some guidance for designing or choosing safer and more suitable ternary organic mixtures prior to their applications for engineering.     

Experimental investigation of the lower flammability limit of volatile liquid fuel-aluminum powder mixtures in air

Aluminum powder was always chosen as an additive to improve the explosive performance. In this work, experiments were performed to investigate the lower flammability limit (LFL) of volatile liquid fuel-aluminum powder mixtures using a 20 L closed spherical stainless steel vessel at a temperature of 20 °C (293 K) and 40 °C (313 K). The volatile liquid fuels tested in the work were diethyl ether (DEE), epoxypropane (PO), n-pentane and n-hexane. DEE, PO and n-pentane are in the liquid phase at room temperature and can easily transition to the gas phase at 40 °C (313 K). Through a series of experiments carried out, it was found that the change in phase would affect the interaction between the components. Aluminum powder always has an inhibitory effect on the flammability of the mixtures when it is mixed with gas-phase fuels. The inhibition effect was most obvious when the aluminum powder concentration reached 200 g/m³. While the interaction between aluminum powder and liquid-phase volatile fuels was promotion and was influenced by the component proportion and the type of the volatile fuels.     

建筑材料及制品燃烧性能试验规范概述

建筑材料和制品燃烧性试验规范对保证建筑物内人的生命安全和财产安全是极为重要的。笔者对美国、加拿大、欧盟、日本以及中国的建筑材料燃烧性能试验规范进行分析、比较和综述。通过研究认为美国和加拿大对建筑材料燃烧性能的要求和试验方法基本相似,他们主要针对材料的燃烧性、火焰传播进行检测;欧盟于2001年颁布了新的燃烧性分级体系,该分级体系包括专门针对铺地材料部分和针对其他所有建筑构件材料和产品部门;日本采用锥形量热计法(ISO5660)将内装饰材料分为不燃、准不燃和阻燃材料3个等级;我国对建筑材料的试验方法包括不燃性试验方法、墙和天花板内装饰材料的三级分级体系和铺地材料两级分级体系。     

Effect of admixture of solid inertant on fire hazard of dust layers oriented at varying degrees of inclination

Unlike metallic dust layers, the layer flammability levels (LFL) of non-metallic dust layers exhibit a wide range from Class 1 (No self-sustained combustion) to Class 6 (explosive combustion). However, determinations of layer flammability have not considered the effect of inclination angle, thereby potentially underestimating fire hazard of combustible dust layers in many industrial situations. In this research, inclined dust layers showed greater fire hazard than did horizontally oriented dust layers. For example, LFL of wood dust jumped from class 3 to class 5 when layers were positioned with an incline. Flame spread rate of PMMA dust layers increased from 1.8 to 3.6 mm/s when the angle of inclination increased from 0 to 40°. Even small amounts of solid inertant significantly decreased surface layer fires. The required amount of inertant to completely inert layer fires was far less than that for smoldering layer fires or dust explosions.     

Theoretical estimation of the lower flammability limit of fuel-air mixtures at elevated temperatures and pressures

We present an approach for predicting the lower flammability limits of combustible gas in air. The influence of initial pressure and temperature on lower flammability limit has been examined in this study. The lower flammability limits of methane, ethylene and propane in air are estimated numerically at the pressure from one to 100 bar and the temperature from ambient to 1200 K. It was found that the predicted LFLs of methane, ethylene and propane decrease slightly with the elevated pressure at the high temperature. The LFLs variation for methane-air mixture is 0.17, 0.18, 0.18 volume% with the initial pressure from one to 100  bar at the initial temperature of 800 K, 1000 K and 1200 K respectively, which is significantly higher than that at lower temperature. And the LFL of methane-air mixture at 1200 K and 100 bar reaches 1.03 volume% which is much lower than that at 1 bar and ambient temperature. On the other hand, the LFLs variation is 0.11–0.12 volume% for ethylene-air mixture and 0.06–0.07 volume% for propane-air mixture with the initial temperature from 800 K to 1200 K at the same range of pressure. The LFL values at high temperatures and pressures represent higher risk of explosion.     

煤中掺比伴生硫化物的自燃特性分析

为了深入探究矿井下伴生硫化物对煤自燃及着火燃烧特性的影响,向原煤中添加不同量的含硫物配制4种不同含硫量的煤样,通过TG实验、DSC测试和XRD分析,研究伴生硫化物对煤自燃及着火燃烧特性的影响规律;基于Coats-Redfern法计算煤中掺加不同伴生硫化物时煤燃烧阶段的活化能。研究结果表明:随着煤中掺比伴生硫化物的增多,煤的特征温度相应减小,而吸氧量、可燃和稳燃指数相应增大,原煤中混入伴生硫化物后更易自燃;随着煤中掺比伴生硫化物的增多,煤燃烧阶段的活化能降低,煤更易着火燃烧;伴生硫化物的主要成分为水绿矾、叶绿矾,这些物质在常温下遇水和氧气能够发生化学循环反应,反应放热促使了煤更易自燃;伴生硫化物在温度高于200℃以后整体表现为放热,在温度为565℃时达到放热峰值,这使得煤燃烧阶段的活化能降低,煤更易燃烧。     

木材在线性增长热流下着火的复合判据研究

为探索木材在热流变化时的着火特点并提出着火判据,通过试验研究了木材在线性增长热流条件下的自发着火性能,测定了泡桐、椿木、榆木和刺槐4种木材的点燃时间、木材表面的入射热流以及试样内部的温度.结果表明.当热流增长率大于等于0.199kw/(m~2·s)时,试验的所有木材均可以被点燃,点燃这些木材的临界热流增长率介于0.065～0.103 kw/(m~2·s).建立了木材着火的计算模型,计算得出木材自发着火时的表面温度约为500℃.根据试验和计算的结果提出了-结合表面温度和临界热流增长率的木材自发着火复合判据.     

Development of novel combustion risk index for flammable liquids based on unsupervised clustering algorithms

Current liquid flammability classification mainly relies on flash point and its risk is largely dependent on consequence and probability. However, combustions of liquefied marine fuels have their uniqueness, leading to a less consistent with the common classification. This work aims at classifying flammable liquids in compression ignition engines for further safety evaluation. Besides liquid flammability characteristics, flame propagation and aerosol formulation are considered. Two unsupervised machine learning clustering algorithms, k-means and spectral clustering, are applied to the collected liquid compounds database. To consider both cluster cohesion and separation, the global mean silhouette value is used to find the optimal number of clusters and to evaluate the clustering performance. The results show that the spectral clustering outperforms k-means on classifying the risk ratings for all proposed models, while the clustering accuracy of the optimal model has been doubled by employing spectral clustering algorithm. Moreover, principal component analysis and star coordinate diagrams are presented to visualize high dimensional data to 2-D graphs. Finally, the overall liquid safety performance is evaluated by a novel combustion risk index via the weight values determined by the information entropy approach. This index can be used to explore inherently safer fuels in the process industries.     

三氧化钼与有机蒙脱土复配体系在膨胀阻燃环氧树脂中的应用

为了提高膨胀阻燃环氧体系的阻燃和抑烟效率,利用聚磷酸铵-季戊四醇-三聚氰胺为膨胀阻燃剂、有机蒙脱土(OMMT)和MoO3为复配协效剂制备了膨胀阻燃环氧树脂,通过极限氧指数(LOI)、UL94、锥形量热仪和烟密度试验研究了膨胀阻燃环氧树脂的阻燃和抑烟性能。结果表明,单独添加OMMT或MoO3均能有效提高膨胀阻燃环氧树脂的LOI并降低燃烧过程中的热释放和生烟量,将二者复配使用还表现出较好的协效作用。添加质量分数1.5%OMMT和1.5%MoO3时,膨胀阻燃氧树脂的LOI达到27.8%,UL94达到V-0级,总释放热(THR)和总产烟量(TSR)相比未添加协效剂的膨胀阻燃环氧树脂分别下降了49.5%和57.8%。热重分析表明,单独添加OMMT或MoO3均能有效提高膨胀阻燃EP的热稳定性和成炭率,二者复配使用则表现出更高的初始分解温度并形成更多的残炭量。扫描电镜和红外光谱分析发现,OMMT和MoO3复配使用能促进膨胀阻燃氧树脂在燃烧过程中形成更多的交联结构以增强炭层的致密性和隔热性能,达到协效阻燃和抑烟作用。     

The explosion parameters of methanol under variable pressures and 423 K

The high-temperature and high-pressure methanol one-step oxidation has been the primary process for the mass production of dimethoxymethane. However, the risk of explosion for this process is still not properly defined. This paper presents new results from the experimental study on the explosion characteristics, including the explosion pressure and the explosion limits for methanol/air mixtures with a variable oxygen level, under an initial pressure between 0.3 MPa and 0.75 MPa and at the initial temperature of 423 K. The upper explosive limits were found to increase along with the initial pressure. If the limits for normal air are known, the oxygen effect on flammability is predictable from the thermal balance method. With a correlation for the pressure effect and a method for the oxygen effect, we can have the flammable range predictable.