Experimental investigation on the lower flammability limits of diethyl ether/ n-pentane/epoxypropane-air mixtures

Diethyl ether (DEE), epoxypropane (PO) and n-pentane have excellent ignition and combustion performance; hence, they have a wide variety of applications in industry and advanced aviation propulsion systems. As these fuels are flammable at normal temperature and pressure, their explosive characteristics need to be explored. In this study, the lower flammability limits (LFLs) of vapor mixtures of DEE/PO/n-pentane in air were measured in 20 L, closed, stainless steel spherical vessels. Experimental results were obtained at ambient atmospheric pressure and an initial temperature of 40 °C. The experimental results show that the LFLs of DEE-air, n-pentane -air, and PO-air are 1.81 vol%, 1.41 vol% and 2.44 vol%, respectively. The LFLs of binary/ternary fuel mixtures under different compositions were tested, and the experimental results are compared with the classical Le Chatelier's formula. The results show that, for the binary fuels (i.e., DEE/PO, DEE/n-pentane, PO/n-pentane)-air mixtures, the maximum difference of the LFLs between Le Chatelier's formula and the experimental results is 6.10%. For the ternary fuels (i.e., DEE/PO/n-pentane)-air mixtures, the maximum difference of the LFLs between the two results is 6.33%. Due to the adiabatic flame temperature of each single fuel mixture being close, the Le Chatelier's formula is applicable for an estimation of the LFL for DEE/PO/n-pentane-air mixtures.     

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.     

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.     

Flash point of biodiesel/glycerol/alcohol mixtures for safe processing and storage

Mixtures of biodiesel, glycerol, and ethanol/methanol are commonly processed and stored in biodiesel production. In this work, non-ideal models are used to calculate the Flash Points (FPs) of binary and ternary mixtures, using data available from different feedstocks. Despite the fact that biodiesel is considered safer than common diesel fuels, results show a synergistic effect of biodiesel/methanol and biodiesel/ethanol mixtures, resulting in a reduction of the flash point of mixtures to values lower than the ones of pure compounds. Most soluble ternary mixtures were found flammable, the only exception being mixtures with a relatively lower alcohol content (45% mol. ethanol or 42% methanol) at temperature lower than 303 K. Accidental increase in temperature can cause domino effect, due to the higher solubility and the formation of new flammable ternary mixtures.     

Validation of a new formula for predicting the lower flammability limit of hybrid mixtures

A correlation of the lower flammability limit for hybrid mixtures was recently proposed by us. The experimental conditions including ignition energy and turbulence which play a primary role in a gas or dust explosion were at fixed values. The sensitivity of such experimental conditions to the accuracy of the proposed formula was not thoroughly discussed in the previous work. Therefore, this work studied the effect of varying the ignition energy and turbulence intensity to the formula proposed in our previous paper. For ignition energy effect, results from methane/niacin mixture demonstrated that the MEC and LFL will not be affected by changing ignition energy. There is no distinguishable difference among gas explosion index (K_G) and dust explosion index (K_St) derived from tests with every ignition energy (2.5 kJ, 5 kJ and 10 kJ) in a 36 L vessel. The proposed formula is independent of ignition energy. For turbulence effect, the proposed formula can have a good prediction of the explosion and non-explosion zone if the ignition delay time is within a certain range. The formula prediction is good as the ignition delay time increases up to 100 ms in this work. Propane/niacin and propane/cornstarch mixtures are also tested to validate the proposed formula. It has been confirmed that the proposed formula predicts the explosion and non-explosion zone boundary of such mixtures.     

Determination of heterogeneous reaction mechanisms: A key milestone in dust explosion modelling

Reaction kinetics is fundamental for modelling the thermal oxidation of a solid phase, in processes such as dust explosions, combustion or gasification. The methodology followed in this study consists in i) the experimental identification of the reaction mechanisms involved in the explosion of organic powders, ii) the proposal of simplified mechanisms of pyrolysis and oxidation, iii) the implementation of the model to assess the explosion severity of organic dusts. Flash pyrolysis and combustion experiments were carried out on starch (22 μm) and cellulose (53 μm) at temperatures ranging from 973 K to 1173 K. The gases generated were collected and analyzed by gas chromatography. In this paper, a semi-global pyrolysis model was developed for reactive systems with low Damköhler number. It is in good agreement with the experimental data and shows that both carbon monoxide and hydrogen are mainly generated during the pyrolysis of the solid, the generation of the latter compound being greatly promoted at high temperature. A simplified combustion model was also proposed by adding two oxidation reactions of the pyrolysis products. In parallel, flame propagation tests were performed in a semi open tube in order to assess the burning velocity of such compounds. The laminar burning velocity of cellulose was determined to be 21 cm s⁻¹. Finally, this model will be integrated to a predictive model of dust explosions and its validation will be based on experimental data obtained using the 20 L explosion sphere. The explosion severity of cellulose was determined and will be used to develop and adjust the predictive model.     

Explosibility of fine graphite and tungsten dusts and their mixtures

To evaluate the explosion hazard of ITER-relevant dusts, a standard method of 20-l-sphere was used to measure the explosion indices of fine graphite and tungsten dusts and their mixtures. The effect of dust particle size was studied on the maximum overpressures, maximum rates of pressure rise, and lower explosive concentrations of graphite dusts in the range 4 μm to 45 μm. The explosion indices of 1 μm tungsten dust and its mixtures with 4 μm graphite dust were measured. The explosibility of these dusts and mixtures were evaluated. The dusts tested were ranked as St1 class. Dust particle size was shown to be very important for explosion properties. The finest graphite dust appeared to have the lowest minimum explosion concentration and be able to explode with 2 kJ ignition energy.     

Effects of ignition energy on fire and explosion characteristics of dilute hybrid fuel in ventilation air methane

Deflagration explosions of coal dust clouds and flammable gases are a major safety concern in coal mining industry. Accidental fire and explosion caused by coal dust cloud can impose substantial losses and damages to people and properties in underground coal mines. Hybrid mixtures of methane and coal dust have the potential to reduce the minimum activation energy of a combustion reaction. In this study the Minimum Explosion Concentration (MEC), Over Pressure Rise (OPR), deflagration index for gas and dust hybrid mixtures (K_st) and explosive region of hybrid fuel mixtures present in Ventilation Air Methane (VAM) were investigated. Experiments were carried out according to the ASTM E1226-12 guideline utilising a 20 L spherical shape apparatus specifically designed for this purpose.Resultsobtained from this study have shown that the presence of methane significantly affects explosion characteristics of coal dust clouds. Dilute concentrations of methane, 0.75–1.25%, resulted in coal dust clouds OPR increasing from 0.3 bar to 2.2 bar and boosting the K_st value from 10 bar m s⁻¹ to 25 bar m s⁻¹. The explosion characteristics were also affected by the ignitors’ energy; for instance, for a coal dust cloud concentration of 50 g m⁻³ the OPR recorded was 0.09 bar when a 1 kJ chemical ignitor was used, while, 0.75 bar (OPR) was recorded when a 10 kJ chemical ignitor was used.For the first time, new explosion regions were identified for diluted methane-coal dust cloud mixtures when using 1, 5 and 10 kJ ignitors. Finally, the Le-Chatelier mixing rule was modified to predict the lower explosion limit of methane-coal dust cloud hybrid mixtures considering the energy of the ignitors.     

Explosion hazards related to hydrogen releases in nuclear facilities

Hydrogen explosion risk needs to be carefully assessed and evaluated in nuclear facilities because of the potential catastrophic consequences: breakdown of safety equipments, failure of containment, dissemination of radioactive materials in the environment.When studying an indoor release, one possible simplification is to assume a perfect gas mixing inside the room. This assumption is effectively often used to evaluate toxic risks in the environment outside a building (Mastellone, Ponte, & Arena, 2003). However, perfect gas mixing assumption is only a rough approximation, as indoor concentrations can largely differ from mean values, due to buoyancy, recirculation zones or obstacles for example.In order to better evaluate the risk of explosion in case of an accidental release of hydrogen, IRSN conducted a numerical study using FLACS CFD software. Several parameters have been studied to identify dangerous situations and draw a representative picture of the risk: room size, position and direction of hydrogen leak, ventilation characteristics. Hydrogen release flow rates used for numerical simulations have been chosen as the highest leak rate which, by applying the assumption of perfect mixing, produces an average concentration in the room equal to hydrogen lower flammability limit (LFL).Simulation results indicate that in some particular configurations, especially for impinging hydrogen jets, hydrogen concentrations can locally be above LFL and then create explosive atmospheres with significant volumes.     

On the explosion and flammability behavior of mixtures of combustible dusts

In the work presented in this paper, the explosion and flammability behavior of combustible dust mixtures was studied. Lycopodium, Nicotinic acid and Ascorbic acid were used as sample dusts.In the case of mixtures of two dusts, the minimum explosive concentration is reproduced well by a Le Chatelier's rule-like formula, whereas the minimum ignition energy is a linear combination of the ignition energies of the pure dusts.An unexpected behavior has been found in relation to the explosion behavior and the reactivity. When mixing Lycopodium and Nicotinic acid or Ascorbic acid, the rate of pressure rise of the mixture is much higher than the rate of pressure rise obtained by linearly averaging the values of the pure dusts (according to their weight proportions), thus suggesting that strong synergistic effects arise; but it is comparable to that of the most reactive dust in the mixture.The observed behavior seems to be linked to the presence of minerals in the Lycopodium particles which catalyze oxidation reactions of Nicotinic acid and Ascorbic acid, as suggested by TG analysis.In the case of mixtures of three dusts, a similar behavior is observed when the concentration of Lycopodium is twice that of the other two dusts.     

Investigations on explosion characteristics of ethyl acetate

In this study, the confined explosion characteristics of ethyl acetate were investigated in a constant volume explosion vessel using the initial pressure of 1–4 bar, the initial temperature of 358–418 K, and the equivalence ratio of 0.8–1.4. It was revealed that the peak explosion pressure and the maximum pressure rise rate of ethyl acetate increased as the initial pressure increased and the initial temperature decreased. The peak explosion pressure and maximum pressure rise rate were obtained at the equivalence ratio of 1.2 due to increased heat release rate. Furthermore, the explosion time decreased as the initial pressure decreased. In summation, EA experimental and theoretical deflagration index were investigated and compared. The experimental deflagration index showed that EA explosion was less dangerous, whereas the theoretical deflagration predicted that the explosion could be more hazardous.     

Experimental study on the minimum explosion concentration of anthracite dust: The roles of O2 mole fraction,inert gas and CH4 addition

The explosion characteristics of anthracite coal dust with/without small amount of CH₄ (1.14 vol %) were investigated by using a 20 L spherical explosion apparatus with an emphasis on the roles of oxygen mole fraction and inert gas. Two methods based on overpressure and combustion duration time were used to determine the minimum explosion concentration (MEC) or the lower explosion limit (LEL) of the pure anthracite coal dust and the hybrid coal-methane mixtures, respectively. The experiment results showed that increasing oxygen mole fraction increases the explosion risk of coal dust: with increasing oxygen mole fraction, the explosion pressure (P_ex) and the rate of explosion pressure rise ((dp/dt)_ex)) increase, while MEC decreases. The explosion risk of anthracite dust was found to be lower after replacing N₂ with CO₂, suggesting that CO₂ has a better inhibition effect on explosion mainly due to its higher specific heat. However, the addition of 1.14% CH₄ moderates the inhibition effect of CO₂ and the promotion effect of O₂ on anthracite dust explosion for some extent, increasing explosion severity and reducing the MEC of anthracite dust. For hybrid anthracite/CH₄ mixture explosions, Barknecht's curve was found to be more accurate and conservative than Chatelier's line, but neither are sufficient from the safety considerations. The experimental results provide a certain help for the explosion prevention and suppression in carbonaceous dust industries.     

Coloured powder potential dust explosions

The use of Coloured powder (Holi powder orcolour dust) has been largely used in India for their festivities. Due to their popularity is extensive around the world since the popularity of the parties and events with this kind of show is increasing considerably. Despite the fact of its extensive use, its highly flammable nature is poorly known. Currently, some serious accidents related to the Coloured powder have been registered. Coloured powder organic nature implies a significant increase in the probability to form an explosive atmosphere as their use includes dust dispersion, leading to explosion hazards as has been previously reported. Moreover, it is important to take into account the effects on the flammability of the additives and the colorings existing in the Coloured powder as they might increase the hazard. To properly understand Coloured powder potential for producing an explosive atmosphere, and the attached risk of dust explosions, several samples were tested. Coloured powder from 6 different manufacturers were gathered. Each manufacturer provided several colours (between 5 and 8) which were characterized through moisture content and particle size determination. Once each sample was characterized, screening tests were performed on each sample determining whether ignition was produced or not. Those screening tests were carried out under certain conditions using the equipment for minimum ignition temperature on cloud determination (0.5 g set at 500 °C and 0.5 bar), and minimum ignition energy determination (using 100 and 300 mJ energies and 900 and 1200 mg). From those test results, important differences were seen between manufacturers, but most important, differences between colours of the same manufacturer were observed. The screening tests allowed the selection of 11 samples that were fully characterized through thermogravimetric analysis, maximum pressure of explosion, K_st, minimum ignition temperature on cloud, and minimum ignition energy. When carrying out thermogravimetric analysis, some samples increased mass at temperatures close to 300 °C and unexpectedly absorbed energy, followed by the expected combustion reaction at higher temperatures. From the obtained results it was noticed that the colour powders that included talcum in its composition did not produce explosion. Flammability and explosion tests, again, showed important differences between manufacturers and colours, and so it was possible to determine the relative flash fire and explosion risks of the various tested powders.     

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.     

Risk-based quantitative method for determining blast-resistant and defense loads of petrochemical buildings

Petrochemical buildings are usually distributed near chemical installations and have a high risk of explosion because of the concentration of people. In order to effectively design and protect buildings against explosion, it is needed to determine the blast-resistant and defense loads reasonably. Based on the theory of risk, a triangular pyramid explosion risk model was established in this study, which combined the overpressure p, duration t, and frequency f of the explosion scene at the same time. The first principle of “acceptable cumulative frequency” and the key principle of “maximum explosion risk” were formulated. According to this method, the explosion risk of eight leakage units with 10 groups of leakage hole size and three dangerous wind directions were obtained. According to the cumulative explosion frequency curve and the explosion risk curve, blast-resistant and defense loads of the four walls were determined quantitatively. Among the four walls, the explosion overpressure were 44.0–74.5 kPa, and the corresponding duration were 34.1–39.1 ms. The cumulative explosion frequency were 2.11E−5 to 8.58E−5 times annually. The explosion risk value were 3.64E−3 to 5.35E−3 kPa·ms annually. The results indicated that it was of great importance for the calculation of the explosion risk to reasonably divide the leakage unit and determine the leakage frequency. The explosion scene and its frequency, the volume of the obstructed region, and the distance of the explosion source were the key variables that affected the explosive load. The final blast-resistant and defense load values were found in the case of the middle hole size leakage. Blast-resistant and defense loads not only met the risk acceptance standard but also considered the overpressure and the duration of explosion. At present, they have been extensively applied in the blast-resistant design and engineering transformation of buildings in SINOPEC.     

Experimental study on the synergistic inhibition effect of nitrogen and ultrafine water mist on gas explosion in a vented duct

In this study, in order to research the synergistic inhibition effect of nitrogen and ultrafine water mist on gas explosion in a vented duct, a semi-confined transparent chamber was designed with the size of 120 × 120 × 840 mm, and the experiments were carried out with stoichiometric methane/air premixed mixture (fraction of methane: 9.5%), adding different fractions of nitrogen and ultrafine water mist. The experimental results showed the following: The combination of nitrogen and ultrafine water mist had a synergistic inhibiting effect on methane/air explosion, which was preferable to the single use of any kind. With the increase of spraying time of water mist and fraction of nitrogen, the initial shape of the explosion flame became snakelike, and at the same time the peak flame propagation speed and peak overpressure decreased significantly. When the nitrogen fraction was increased to 10% and the mist spraying time was increased to 2min, synergistic inhibiting effect on overpressure was high efficient. However, with the increase of spraying time of water mist and fraction of nitrogen going on, the amount of increase of explosion inhibition efficiency was gradually reduced.     

Fast and tiny: A model for the flame propagation of nanopowders

To avoid the influence of external parameters, such as the vessel volume or the initial turbulence, the explosion severity should be determined from intrinsic properties of the fuel-air mixture. Therefore, the flame propagation of gaseous mixtures is often studied in order to estimate their laminar burning velocity, which is both independent of external factors and a useful input for CFD simulation. Experimentally, this parameter is difficult to evaluate when it comes to dust explosion, due to the inherent turbulence during the dispersion of the cloud. However, the low inertia of nanoparticles allows performing tests at very low turbulence without sedimentation. Knowledge on flame propagation concerning nanoparticles may then be modelled and, under certain conditions, extrapolated to microparticles, for which an experimental measurement is a delicate task. This work focuses on a nanocellulose with primary fiber dimensions of 3 nm width and 70 nm length. A one-dimensional model was developed to estimate the flame velocity of a nanocellulose explosion, based on an existing model already validated for hybrid mixtures of gas and carbonaceous nanopowders similar to soot. Assuming the fast devolatilization of organic nanopowders, the chemical reactions considered are limited to the combustion of the pyrolysis gases. The finite volume method was used to solve the mass and energy balances equations and mass reactions rates constituting the numerical system. Finally, the radiative heat transfer was also considered, highlighting the influence of the total surface area of the particles on the thermal radiation. Flame velocities of nanocellulose from 17.5 to 20.8 cm/s were obtained numerically depending on the radiative heat transfer, which proves a good agreement with the values around 21 cm/s measured experimentally by flame visualization and allows the validation of the model for nanoparticles.     

Explosion prevention and weighting analysis on the inerting effect of methane via grey entropy model

Explosion prevention is vital for process safety and daily life. In practice, inerting is viewed as an ideal method to reach basic explosion prevention as well as to diminish flammability risk in normal operation, storage, and transportation of materials. This study deals with the inerting effect on the explosion range for methane via grey entropy model, comparatively detected under the different inert gases of nitrogen (N₂), argon (Ar), and carbon dioxide (CO₂), which have various loading inerting concentrations: 10 (90 vol% air), 20 (80 vol% air) and 25 vol% (75 vol% air). The inert influences were determined via the experimental 20-L-apparatus investigations under 1 atm, 30 ^OC, combined with the grey entropy model, which is one of the most prevailingly used grey system theories for weighting analysis and decision-making of the fire and explosion assessment for practical operations. The results indicated that CO₂ had better inerting capacity than the others, as derived from our grey entropy theoretical soft computing calculations. Through the combination of the grey entropy weighting analysis model and the flammability investigations in this study, the concluded decision-making was feasible and useful for the practical applications of inert gases for preventing fire and explosion hazards in relevant processes.     

A constant pressure dust explosion experiment

A new apparatus has been designed for investigating flame propagation in turbulent dust clouds at near constant pressure conditions. The experimental approach is inspired by the classical soap bubble method for measuring burning velocities in gaseous mixtures. Combustible dust is dispersed with pressurised air to form an explosive mixture inside a transparent latex balloon. After a certain delay time, the turbulent dust cloud is ignited by a 40 J chemical igniter. A digital high-speed video camera records the propagating flame and the expansion of the balloon. Experiments were performed with two types of dust, Lycopódium spores and maize starch, as well as with propane–air mixtures under initially quiescent or turbulent conditions. Although the results are primarily qualitative in nature, they nevertheless demonstrate fundamental differences between premixed combustion of gaseous mixtures, and ‘premixed combustion with non-premixed substructures' in mechanical suspensions of solid particles dispersed in air. The discussion highlights some fundamental challenges for future dust explosion research.     

Inhibiting effects of gas–particle mixtures containing CO2, Mg(OH)2 particles,and NH4H2PO4 particles on methane explosion in a 20-L closed vessel

The main risk factors from methane explosion are the associated shock waves, flames, and harmful gases. Inert gases and inhibiting powders are commonly used to prevent and mitigate the damage caused by an explosion. In this study, three inhibitors (inert gas with 8.0 vol% CO₂, 0.25 g/L Mg(OH)₂ particles, and 0.25 g/L NH₄H₂PO₄ particles) were prepared. Their inhibiting effects on methane explosions with various concentrations of methane were tested in a nearly spherical 20-L explosion vessel. Both single-component inhibitors and gas–particle mixtures can substantially suppress methane explosions with varying degrees of success. However, various inhibitors exhibited distinct reaction mechanisms for methane gas, which indicated that their inhibiting effects for methane explosion varied. To alleviate amplitude, the ranking of single-component inhibitors for both explosion pressure (P_ex) and the rate of explosion pressure rise [(dP/dt)_ex] was as follows: CO₂, NH₄H₂PO₄ particles, and Mg(OH)₂ particles. In order of decreasing amplitude, the ranking of gas‒particle mixtures for both P_ex and (dP/dt)_ex was as follows: CO₂–NH₄H₂PO₄ mixture, CO₂‒Mg(OH)₂ mixture, and pure CO₂. Overall, the optimal suppression effect was observed in the system with the CO₂–NH₄H₂PO₄ mixture, which exhibited an eminent synergistic effect on methane explosions. The amplitudes of P_ex with methane concentrations of 7.0, 9.5, and 11.0 vol% decreased by 37.1%, 42.5%, and 98.6%, respectively, when using the CO₂–NH₄H₂PO₄ mixture. In addition, an antagonistic effect was observed with CO₂‒Mg(OH)₂ mixtures because MgO, which was generated by the thermal decomposition of Mg(OH)₂, can chemically react with water vapor and CO₂ to produce basic magnesium carbonate (xMgCO₃·yMg(OH)₂·zH₂O), thereby reducing the CO₂ concentration in a reaction system. This research revealed the inhibiting effects of gas‒particle mixtures (including CO₂, Mg(OH)₂ particles, and NH₄H₂PO₄ particles) on methane explosions and provided primary experimental data.