Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

Supercritical water oxidation of ion exchange resins: Degradation mechanisms

Spent ion exchange resins are radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation could offer a viable treatment alternative to destroy the organic structure of resins and contain radioactivity. IER degradation experiments were carried out in a continuous supercritical water reactor. Total organic carbon degradation rates in the range of 95–98% were obtained depending on operating conditions. GC–MS chromatography analyses were carried out to determine intermediate products formed during the reaction. Around 50 species were identified for cationic and anionic resins. Degradation of polystyrenic structure leads to the formation of low molecular weight compounds. Benzoic acid, phenol and acetic acid are the main compounds. However, other products are detected in appreciable yields such as phenolic species or heterocycles, for anionic IERs degradation. Intermediates produced by intramolecular rearrangements are also obtained. A radical degradation mechanism is proposed for each resin. In this overall mechanism, several hypotheses are foreseen, according to HOO radical attack sites.     

Reliability and applicability of empirical equations in predicting the reduced explosion pressure of vented gas explosions

Explosions caused by the rapid release of energy from the expansion of burnt gases, along with an associated pressure rise, in an enclosure can be mitigated by venting. Many empirical equations have been derived based on vented gas deflagration phenomena. In the present paper, four empirical equations for gas venting were reviewed, i.e., NFPA 68, the European Standard (EN 14994), Molkov et al. and Bradley and Mitcheson in order to assess their reliability and applicability for predicting the reduced explosion pressure (P_red) of propane-air, methane-air and hydrogen-air mixtures at three different chamber-scale volumes. The results showed that the NFPA 68 correlation is the most appropriate method for predicting P_red, while Bradley and Mitcheson gave values closer to those of experimental data for propane-air mixtures in medium and larger chambers, respectively. However, none of the predicted correlations was able to provide a reasonable prediction of P_red in a hydrogen-air explosion. In addition, these predicted correlations showed greater discrepancies in P_red values in the presence of vent area, ignition position and obstacles.     

Effect of scale on the explosion of methane in air and its shockwave

Explosion experiments using premixed gas in a duct have become a significant method of investigating methane-air explosions in underground coal mines. The duct sizes are far less than that of an actual mine gallery. Whether the experimental results in a duct are applicable to analyze a methane-air explosion in a practical mine gallery needed to be investigated. This issue involves the effects of scale on a gas explosion and its shockwave in a constrained space. The commercial software package AutoReaGas, a finite element computational fluid dynamics (CFD) code suitable for gas explosions and blast problems, was used to carry out the numerical simulation for the explosion processes of a methane-air mixture in the gallery (or duct) at various scales. Based on the numerical simulation and its analysis, the effect of scale on the degree of correlation with the real situation was studied for a methane-air explosion and its shockwave in a square section gallery (or duct). This study shows that the explosion process of the methane-air mixture relates to the scales of the gallery or duct. The effect of scale decreases gradually with the distance from the space containing the methane-air mixture and the air shock wave propagation conforms approximately to the geometric similarity law in the far field where the scaled distance (ratio of the propagation distance and the height (or width) of the gallery section) is over 80.     

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.     

密闭空间内天然气混合及爆炸传播规律研究

为研究密闭容器内甲烷-空气不均匀分布对混合气体燃烧的影响,将数值模拟和实验相结合,发现在重力作用下混合气体浓度分布不均匀,长径比越大的容器,混合气体浓度分布梯度越大。混合气体浓度分布影响气体火焰传播规律。宏观浓度为5%的甲烷与空气混合后,容器上部甲烷浓度高于5%,在该处点火时非均匀混合甲烷-空气火焰传播较快,非均匀混合气体的爆炸压力比均匀混合气体压力上升快,且分层混合气体的超压峰值高于均匀混合气体的值。由于浓度分布不均匀,点火位置影响甲烷/空气火焰传播的规律。     

湍流状态下甲烷爆炸特性的实验研究

利用20L近球形气体爆炸反应装置,测试甲烷在宏观静止和湍流两种不同状态下的爆炸特性。实验结果表明:甲烷的爆炸极限受其流动状态的影响不明显;湍流状态下甲烷爆炸压力Pm和爆炸压力上升速率(dp/dt)m较宏观静止状态明显增大,爆炸压力峰值时间tm明显缩短,其中爆炸压力上升速率受湍流影响较为显著;甲烷浓度不同,其爆炸受湍流影响的程度也不同,较高浓度(11%～16%)时的Pm受湍流的影响程度较大,越靠近最佳浓度(dp/dt)m和tm受湍流的影响程度越大;同一浓度下Pm和(dp/dt)m随着湍流的加强而增大,tm则缩短。该研究表明,避免和减少湍流对矿井瓦斯爆炸过程的抑制具有重要作用。     

Experimental and numerical investigation of constant volume dust and gas explosions in a 3.6-m flame acceleration tube

This paper describes an experimental investigation of turbulent flame propagation in propane-air mixtures, and in mechanical suspensions of maize starch dispersed in air, in a closed vessel of length 3.6 m and internal cross-section 0.27 m × 0.27 m. The primary motivation for the work is to gain improved understanding of turbulent flame propagation in dust clouds, with a view to develop improved models and methods for assessing explosion risks in the process and mining industries. The study includes computational fluid dynamics (CFD) simulations with FLACS and DESC, for gas and dust explosions respectively. For initially quiescent propane-air mixtures, FLACS over-predicts the rate of combustion for fuel-lean mixtures, and under-predicts for fuel-rich mixtures. The simulations tend to be in better agreement with the experimental results for initially turbulent gaseous mixtures. The experimental results for maize starch vary significantly between repeated tests, but the subset of tests that yields the highest explosion pressures are in reasonable agreement with CFD simulations with DESC.     

泡沫镍对甲烷-空气预混气体爆燃超压影响的研究

为了有效抑制气体爆炸时产生的冲击波强度,设计加工了内部截面为110 mm×80 mm,长500 mm的爆炸实验管道,利用高频动态压力传感器,对比研究了泡沫镍在管道内的安放位置对甲烷-空气预混气体爆炸的影响。结果表明:当把泡沫镍铺设在管道中间位置时其对爆炸超压的抑制效果最好,其次是放置在管道的尾部,效果最差的是将多孔材料放置在管道的前部。     

Effects of premixed methane concentration on distribution of flame region and hazard effects in a tube and a tunnel gas explosion

Study of flame distribution laws and the hazard effects in a tunnel gas explosion accident is of great importance for safety issue. However, it has not yet been fully explored. The object of present work is mainly to study the effects of premixed gas concentration on the distribution law of the flame region and the hazard effects involving methane-air explosion in a tube and a tunnel based on experimental and numerical results. The experiments were conducted in a tube with one end closed and the other open. The tube was partially filled with premixed methane-air mixture with six different premixed methane concentrations. Major simulation works were performed in a full-scale tunnel with a length of 1000 m. The first 56 m of the tunnel were occupied by methane–air mixture. Results show that the flame region is always longer than the original gas region in any case. Concentration has significant effects on the flame region distribution and the explosion behaviors. In the tube, peak overpressures and maximum rates of overpressure rise (dp/dt)_max for mixtures with lower and higher concentrations are great lower than that for mixtures close to stoichiometric concentration. Due to the gas diffusion effect, not the stoichiometric mixture but the mixture with a slightly higher concentration of 11% gets the highest peak overpressure and the shock wave speed along the tube. In the full-scale tunnel, for fuel lean and stoichiometric mixture, the maximum peak combustion rates is achieved before arriving at the boundary of the original methane accumulation region, while for fuel rich mixture, the maximum value appears beyond the region. It is also found that the flame region for the case of stoichiometric mixture is the shortest as 72 m since the higher explosion intensity shortens the gas diffusion time. The case for concentration of 13% can reach up to a longest value of 128 m for longer diffusion time and the abundant fuel. The “serious injury and death” zone caused by shock wave may reach up to 3–8 times of the length of the original methane occupied region, which is the widest damage region.     

Effect of scale on flame speeds of methane-air

Explosions are the main types of accidents causing casualties in underground coal mines. Research on the mechanisms of gas explosions is needed as a basis for the development of techniques and strategies for explosion prevention, suppression, and mitigation. The prevention of loss in explosion accidents and inquiries into their causes require understanding of the explosion process of methane in air. Because of the high cost and safety issues in full scale experiments, the experiments with small scale ducts have become a key alternative approach. Whether the experimental results at small scales agree with those at full scales needs to be investigated to validate the significance of the experimental results at small scale. Numerical simulation was used to obtain the explosion characteristics of a methane-air mixture in a gallery or duct. If the grid size is too fine in the numerical simulation for a methane-air explosion it is difficult to calculate using the present computer resource. If the grid size is too coarse, the considerable error may result. The effect of grid size on results of calculation depends on the scenario being investigated. The effect of grid sizes on simulation accuracy was analyzed in this work. The overpressure and temperature distributions and the flame propagation for the deflagration of methane-air mixtures in a gallery or duct were obtained by the AutoReaGas code at three different scales. The geometry of investigated objects and the grids in the calculation domain were similar in the three cases. The calculated overpressures vary with the scale. The calculated temperatures do not vary with the scale for the three cases.     

可燃气体爆炸破坏效应的试验研究

借助高速摄像机及ProAnalyst软件,研究可燃气体体积分数和障碍物对可燃气体爆炸破坏力的影响。测定不同体积分数下的甲烷-空气预混气体爆炸冲击波超压,和爆炸火焰波在有无乒乓球方向传播的平均速度。试验结果表明:超压和平均速度均随着甲烷体积分数的增加呈现先增大后减小的变化趋势,其最大值均出现在甲烷体积分数为10%～11%之间;同一体积分数下的甲烷-空气预混气体爆炸火焰波在有乒乓球方向传播的平均速度比没有乒乓球方向传播的平均速度大。根据试验结果,推导出可燃气体爆炸冲击波超压和爆炸火焰波传播平均速度与可燃气体体积分数之间的函数关系,并得出障碍物对爆炸火焰波传播的加速作用随着体积分数的增加呈现先加强后减弱的变化趋势。     

Insight into vented explosion mechanism and premixed flame dynamics in linked vessels: Influence of membrane thickness and blocking rate

To effectively prevent and mitigate explosion hazards and casualties, relief venting of flammable gas explosions has been applied in production processes in a broad variety of industries. This work conducted fully vented experiments to investigate the influence of venting membrane thickness, and partially vented experiments to investigate the influence of baffle blocking rate on the explosion characteristics of 9.5 vol% methane-air mixtures in linked vessels with a 0.5 m long vented duct. Results indicate that the membrane thickness and blocking rate for the two types of vented explosions significantly affected the explosion overpressure. The smaller the membrane thickness and blocking rate, the lower the explosion overpressure. Secondary explosions were observed in the vented duct through experiments and a weaker explosion flame appeared at a small blocking rate of 20%. With the further increase in the blocking rate, the flame became extremely weak, and no secondary explosions occurred. The overpressure evolution process at different positions in the explosion duct and secondary explosion phenomenon in the vented duct were investigated. This work could probably serve as an important reference for the selection of technical parameters of explosion venting in the practical industrial processes.     

Large-scale dust explosions in vessel-pipe systems

This study investigates dust explosions in vessel-pipe systems to develop a better understanding of dust flame propagation between interconnected vessels and implications for the proper application of explosion isolation systems. Cornstarch dust explosions were conducted in a large-scale setup consisting of a vented 8-m³ vessel and an attached pipe with a diameter of 0.4 m and a length of 9.8 m. The ignition location and effective dust reactivity were varied between experiments. The experimental results are compared against previous experiments with initially quiescent propane-air mixtures, demonstrating a significantly higher reactivity of the dust explosions due to elevated initial turbulence, leading to higher peak pressures and faster flame propagation. In addition, a physics-based model developed previously to predict gas explosion dynamics in vessel-pipe systems was extended for dust combustion. The model successfully predicts the pressure transients and flame progress recorded in the experiments and captures the effects of ignition location and effective dust reactivity.     

Propane-air mixture deflagration hazard with different ignition positions and restraints in large-scale venting chamber

In order to better assess the hazards of explosion accidents, propane-air mixture deflagrations were conducted in a large-scale straight rectangular chamber (with a cross-section of 1.5 m × 1.5 m, length of 10 m, and total volume of 22.5 m³). The effect of initial volume, ignition position, and initial restraints on the explosion characteristics of the propane-air mixtures was investigated. The explosion overpressure, flame propagation, and flame speed were obtained and the computational fluid dynamics (CFD) software was used to simulate the flame-propagation process and field flow for auxiliary analysis. The hazards of large-scale propagation explosion under weak and strong constraints were evaluated and the different phases of flame propagation under weak and strong constraints were discriminated. Results indicate that the hazards caused by propane deflagration under weak constraint are mainly caused by flame spread. And the maximum overpressure under strong constraint appeared at the front part of the chamber under the large-scale condition, which is consistent with the previous small-scale test. Moreover, the simulations of flame structures under weak and strong constraint are in good agreement with experimental results, which furthers the understanding of large-scale propane deflagration under different initial conditions in large-scale spaces and provides basic data for three-dimensional CFD model improvement.     

Evaluation of the effectiveness of toe board energy-absorbing material for foot,ankle, and lower leg injury reduction

Objective: Since 2000, numerous improvements have been made to the National Association for Stock Car Auto Racing, Incorporated (NASCAR®) driver restraint system, resulting in improved crash protection for motorsports drivers. Advancements have included seats, head and neck restraints (HNRs), seat belt restraint systems, driver helmets, and others. These enhancements have increased protection for drivers from severe crash loading. Extending protection to the driver's extremities remains challenging. Though the drivers’ legs are well contained for lateral and vertical crashes, they remain largely unrestrained in frontal and frontal oblique crashes.

Method: Sled testing was conducted for the evaluation of an energy-absorbing (EA) toe board material to be used as a countermeasure for leg and foot injuries. Testing included baseline rigid toe boards, tests with EA material–covered toe boards, and pretest positioning of the 50th percentile male frontal Hybrid III anthropomorphic test device (ATD) lower extremities. ATD leg and foot instrumentation included foot acceleration and tibia forces and moments.

Results: The sled test data were evaluated using established injury criteria for tibial plateau fractures, leg shaft fractures, and calcaneus, talus, ankle, and midfoot fractures.

Conclusion: A polyurethane EA foam was found to be effective in limiting axial tibia force and foot accelerations when subjected to frontal impacts using the NASCAR motorsport restraint system.     

管道燃气爆炸特性实验研究

管道是化工及油气储运系统的重要组成部分,却时常受燃烧爆炸事故的威胁,因此对管道中燃气燃烧爆炸特性与规律的研究就十分必要。以甲烷作为研究对象,采用压力传感器以及火焰传感器等对水平封闭管道内甲烷-空气预混燃烧爆炸进行了实验研究,通过大量实验来研究可燃气体爆炸压力与火焰及其传播变化规律。根据实验结果将超压以及气体燃烧的变化情况,对前驱冲击波与火焰面的相对时间及相对位置关系进行了分析。结果显示,管道中会产生前驱压力波,并超前火焰阵面甲烷气体在管道传播过程中,出现冲击波反压射、波叠加及反冲现象,压力的持续时间较火焰光信号持续时间长。所做的工作为油气受限空间中燃气燃烧爆炸特性与规律的进一步研究及工业防爆抑爆技术及工艺的实施、系统设计以及关键参数计算提供了理论依据。     

Effective method of predicting confined pressure behavior under isotropic turbulence

Explosion pressure prediction is indispensable to ensure process safety against accidental gas explosions. This work is aimed at establishing a theoretical method for predicting confined methane-air explosion pressure under isotropic turbulence. The results indicated that the pressure rise rate becomes significantly increased by the existence of isotropic turbulence, which effect on peak value of explosion pressure is negligible. Among various models of turbulent burning velocity, the calculated pressure rise rate using Chiu model, Williams model and Liu model is relatively closer to experimental value. With the increase of turbulent integral length and RMS turbulent fluctuation velocity, the pressure rise rate becomes increased continuously. The influence of adiabatic compression and isothermal compression on pressure rise rate could be ignored. To predict explosion pressure in a more accurate way, the dynamic variation of turbulent integral length and RMS turbulent fluctuation velocity should be considered in the future.