Decomposing detonation and deflagration properties of ozone/oxygen mixtures

In this study, the decomposing detonation and deflagration properties of ozone/oxygen mixtures of up to 20 vol.% of ozone in oxygen under high pressure of up to 1.0 MPa in a tube were experimentally investigated. The mixtures were ignited by an electric spark at the end of the tube. Flame propagation properties such as flame velocity and pressure were measured with thermocouples and piezo electric transducers mounted along the tube. Slow and constant flame propagation profiles were obtained. We also investigated the quenching ability of a wire gauze as well as the concentration limit for flame propagation. However, in spite of slow flame propagation velocity and easy flame quenching properties under these experimental conditions, direct initiation of detonation by the driver detonation of the stoichiometric oxy-hydrogen mixture was easily achieved at much lower concentrations than the limit of deflagration. The observed detonation properties, such as wave velocity and pressure, agreed fairly well with C–J calculated values. The detonation velocity (900–1200 m/s) and the pressure ratio to initial pressures (5–9.5) were not affected by the initial pressure of the mixtures. Near the detonation limit, typical spinning detonations with oscillatory pressure waves were observed.     

Explosion properties of highly concentrated ozone gas

The explosive self-decomposition characteristics of gaseous ozone with a concentration of up to almost 100 vol% were quantitatively investigated using a closed system with an electric spark device. The lower self-decomposition (explosion) limit for ozone diluted with oxygen at room temperature and atmospheric pressure was 10–11 vol%, and so ozone at more than 10–11 vol% will lead to an explosive chain decomposition reaction leading to its complete conversion to oxygen in a vessel. The lower explosion limit shifts to a higher concentration with a decrease in pressure. The limit was about 80 vol% under a reduced pressure of 10 Torr. We also confirmed that explosion trigger energy (minimum ignition energy) is strongly dependent on ozone concentration and pressure. For example, the minimum trigger energy for 15 vol% ozone at a pressure of 76 Torr (about 220 mJ) was more than 20-fold that at atmospheric pressure (about 10 mJ), and that for 13 vol% ozone (about 580 mJ) was approximately 30 times higher than that for 20 vol% (about 20 mJ) at the same pressure of 76 Torr. Moreover, the physical characteristics of the trigger energy sources (e.g. spark gap and electrode tip angle) leading to the decomposition (explosion) of ozone were investigated under various conditions.     

An influence of oxygen content in an oxidizing atmosphere on inhibitive action of fluorinated agents on a hydrogen flame

An experimental investigation of the influence of inhibitors of various chemical natures on flammability limits in mixtures H₂+oxidizer (O₂+N₂)–suppressant (C₂HF₅; CHF₃; C₄F₁₀; inhibitor AKM, which is a mixture of olefins) was carried out. Compositions of N₂ and O₂ with elevated (25 vol%) and reduced (15 vol%) oxygen concentrations and air were used as oxidizing atmospheres. Experiments were done at room temperature and atmospheric pressure. Flammability limits were determined in a closed vessel of volume of 4.2 dm³ (internal diameter 20 cm). Mixtures were prepared immediately in the preliminary evacuated reaction vessel by partial pressures. The mixtures were ignited by an electrical spark of energy near 1 J in the center of the reaction vessel. A flame propagation was detected by a pressure transducer. Twelve flammability curves were measured, which allowed to compare effectiveness of the inhibitors at various oxygen contents in the atmosphere. A qualitative analysis of the obtained results was done, which showed an important role of an inhibitor regeneration.     

The effect of vent ducts on the reduced explosion pressures of vented dust explosions

An investigation into the effects of vent ducts on reduced explosion pressures is described. Experiments were made using an 18.5m³ explosion vessel and a modified 20 1 sphere, with dusts having K_st values ranging from 144 bar ms⁻¹ to 630 bar ms⁻¹. The vent area/vessel volume ratio bursting pressure of the vent cover, and the length to diameter ratio of the vent duct have been varied. Straight vent ducts, and ducts containing sharp 45° and 90° bends have been used.A simple model to describe the effect of vent ducts on the reduced explosion pressure has been derived and compared with the experimental results. Agreement is shown to be satisfactory in nearly all cases. A comparison between the experimental results and guidance on the effect of vent ducts already available in the literature is discussed.     

Effect of initial pressure on explosion characteristics of 2, 3, 3, 3–tetrafluoropropene

With the popularity of refrigerants in the process industries, the potential safety problems caused by the use of refrigerants have attracted worldwide attention as people have realized their inherent explosion characteristics of refrigerants. This paper studied the explosion characteristics of refrigerant 2, 3, 3, 3–tetrafluoropropene (R1234yf) at different concentrations and initial pressures based on a 20 L experimental apparatus. The experimental results illustrated the peak overpressure of R1234yf increased with the rise of initial pressure. At a constant ambient temperature of 25 °C, the maximum rate of pressure rise and deflagration index showed an N-shaped trend with the increase of the refrigerant concentration from 6.8% to 10%. The maximum rate of pressure rise and deflagration index increased first and then decreased with the increase of the refrigerant concentration at atmospheric pressure, while they presented an M-shaped trend at pressurization condition. The peak overpressure, the maximum rate of pressure rise, and deflagration index reached 0.742 MPa, 4.04 MPa s⁻¹, and 1.1 MPa.m.s⁻¹ with a refrigerant concentration of 7.6%, respectively, which were less than those of refrigerant propane and difluoromethane (R32) at the optimal concentration. Furthermore, R1234yf exhibited better safety performance compared with refrigerant R32 in the same flammability classification.     

Ignitability characteristics of aluminium and magnesium dusts that are generated during the shredding of post-consumer wastes

The authors investigated the ignitability of aluminium and magnesium dusts that are generated during the shredding of post-consumer waste. The relations between particle size and the minimum explosive concentration, the minimum ignition energy, the ignition temperature of the dust clouds, etc. the relation between of oxygen concentration and dust explosion, the effect of inert substances on dust explosion, etc. were studied experimentally.

The minimum explosive concentration increased exponentially with particle size. The minimum explosive concentrations of the sample dusts were about 170 g/m³ (aluminium: 0–8 μm) and 90 g/m³ (magnesium: 0–20 μm). The minimum ignition energy tended to increase with particle size. It was about 6 mJ for the aluminium samples and 4 mJ for the magnesium samples. The ignition temperature of dust clouds was about 750 °C for aluminium and about 520 °C for magnesium. The lowest concentrations of oxygen to produce a dust explosion were about 10% for aluminium and about 8% for magnesium. A large mixing ratio (more than about 50%) of calcium oxide or calcium carbonate was necessary to decrease the explosibility of magnesium dust. The experimental data obtained in the present investigation will be useful for evaluating the explosibility of aluminium and magnesium dusts generated in metal recycling operations and thus for enhancing the safety of recycling plants.     

Correlation between flash points and vapor pressures of organic compounds

Correlations between flash points and vapor pressures at 25 °C for pure organic compounds were investigated. It was found that classification of organic compounds according to their chemical-structural characteristics (e.g., functional groups) was necessary for the correlation study. Under this classification, linearity seems to be the most appropriate correlation to explain the relationship between the inverse of flash points (°K) and the logarithm of vapor pressures (mm Hg) at 25°C for pure organic compounds. A test study to evaluate the validity of a regression line as an estimation of an unknown flash point from a known vapor pressure was carried out with a data set containing 31 alkanes and aromatics; 55% of the flash points were predicted within ±5°Cand89% were within ±10°C. Within limits of ± 5 to 10°C the procedure is useful but should be improved.     

Investigation of the use of a closed pressure vessel test for estimating condensed phase explosive properties of organic compounds

Following the indications of earlier work, the use of a closed pressure vessel test (a mini-autoclave system) to estimate the explosive properties of organic compounds has been investigated. The dependent variable was an explosivity ranking derived from the results of a propagation of detonation test, a heating under confinement test and a deflagration test. Tentative criteria have been derived to allow the following conclusions:• Not detonable• Not Class 1• No explosive properties with respect to transport classificationThe criteria are based upon the maximum rate of pressure rise observed in the mini-autoclave and the temperature at which this occurs. They offer a more efficient screen than the decomposition energy criteria which are currently used for initial assessment of explosive properties. The importance of event temperature suggests that existing classification tests may be underestimating heating under confinement and deflagration hazards. In this case, maximum rates of pressure rise from a closed pressure vessel test might be a better basis of classification, at least for supply if not transport. Further work is necessary to test the proposed screening criteria and to assess the use of a closed pressure vessel test as a means of classification.     

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.     

Explosibility of hydrogen–graphite dust hybrid mixtures

To evaluate the hazard of combined hydrogen/dust explosions under severe accident conditions in International Thermonuclear Experimental Reactor (ITER), standard method of 20-L-sphere was used to measure the explosion indices of 4-μm fine graphite dust in lean hydrogen/air mixtures. The mixtures were ignited by a weak electric spark. The tested fuel concentrations were 8–18 vol% H₂ and 25–250 g/m³ dust. If the hydrogen content is higher than 10 vol%, the dust constituent can be induced to explode by the hydrogen explosion initiated by a weak electric spark. Depending on the fuel component concentrations, the explosions proceed in either one or two stages. In two-stage explosions occurring at low hydrogen and dust concentrations, the mixture ignition initiates first a fast hydrogen explosion followed by a slower phase of the dust explosion. With increasing dust concentration, the dust explodes faster and can overlap the hydrogen-explosion stage. At higher hydrogen concentrations, the hybrid mixtures explode in one stage, with hydrogen and dust reacting at the same time scale. Maximum overpressures of hybrid explosions are higher than those observed with hydrogen alone; maximum rates of pressure rise are lower in two-phase explosions and, generally, higher in one-stage explosions, than those characteristic of the corresponding H₂/air mixtures.     

水平管道泄爆面开启压力对甲烷爆燃压力的影响*

为了研究泄爆面不同开启压力对甲烷爆燃压力的影响,针对受限空间内甲烷/空气混合物爆燃传播过程,建立由水平管道构成的数值模型。研究结果表明:水平管道内存在爆燃压力积聚和泄放的双重效应,随着泄爆面开启压力的增加,测点爆燃压力峰值增大而且测点间爆燃压力峰值差异逐渐减小;在泄爆面不同开启压力条件下,泄压效应造成泄爆面及外部空气域爆燃压力衰减,随着泄爆面开启压力的增加,泄爆面开启时间近似呈线性增大;与水平管道内和泄爆面附近测点相比,水平管道外侧测点的爆燃压力峰值和振荡幅值均显著衰减,而且随着泄爆面开启压力的增加,测点爆燃压力峰值及测点间爆燃压力峰值差异均逐渐增大。     

Unified correlations for vent sizing of enclosures at atmospheric and elevated pressures

Innovative vent sizing technology is presented for explosion safety design of equipment at atmospheric and elevated initial pressures. Unified correlations for vent sizing are suggested. They are modifications of previously reported correlations verified thoroughly for experimental data on vented gaseous deflagrations under different conditions but only at initial atmospheric pressure. Suggested correlations are based on experimental data on vented deflagrations of quiescent and turbulent propane–air mixtures at initial pressures up to 0.7 MPa. Typical values of turbulence factor and deflagration–outflow interaction number are obtained for experimental vented deflagrations at initial pressures higher than atmospheric.

“Blind” examination of new vent sizing technology on another set of experiments with methane–air and propane–air mixtures has shown that predictions by suggested vent sizing technology are better than by the NFPA 68 guide for “Venting of Deflagrations”.

In the development of recently reported results for initial atmospheric pressure it has been concluded that the innovative vent sizing technology is more reliable compared to the NFPA 68 guide at elevated initial pressures as well. Moreover it is crucial that the calculation procedure remains the same for arbitrary deflagration conditions.     

Propagation Characteristics of Gas Explosion in Linked Vessels Based on DDT Criteria

To study the occurrence conditions and propagation characteristics of deflagration to detonation transition (DDT) in linked vessels, two typical linked vessels were investigated in this study. The DDT of the methane–air mixture under different pipe lengths and inner diameters was studied. Results showed that the CJ detonation pressure of the methane–air mixture was 1.86 MPa, and the CJ detonation velocity was 1987.4 m/s. Compared with a single pipe, the induced distance of DDT is relatively short in the linked vessels. With the increase in pipeline length, DDT is more likely to occur. Under the same pipe diameter, the DDT induction distance in the vessel–pipe–vessel structure is shorter than that in the vessel–pipe structure. With the increase in pipeline diameter, the length of the pipe required to form the DDT is reduced. For linked vessels in which detonation formed, four stages, namely, slow combustion, deflagration, deflagration to detonation, and stable detonation, occurred in the vessels. Moreover, for a pipe diameter of 60 mm and a length of 8 m, overdriven detonation occurred in the vessel–pipe–vessel structure.     

CFD modelling of hydrogen release, dispersion and combustion for automotive scenarios

The paper describes the analysis of the potential effects of releases from compressed gaseous hydrogen systems on commercial vehicles in urban and tunnel environments using computational fluid dynamics (CFD). Comparative releases from compressed natural gas systems are also included in the analysis.

This study is restricted to typical non-articulated single deck city buses. Hydrogen releases are considered from storage systems with nominal working pressures of 20, 35 and 70 MPa, and a comparative natural gas release (20 MPa). The cases investigated are based on the assumptions that either fire causes a release via a thermally activated pressure relief device(s) (PRD) and that the released gas vents without immediately igniting, or that a PRD fails. Various release strategies were taken into account. For each configuration some worst-case scenarios are considered.

By far the most critical case investigated in the urban environment, is a rapid release of the entire hydrogen or natural gas storage system such as the simultaneous opening of all PRDs. If ignition occurs, the effects could be expected to be similar to the 1983 Stockholm hydrogen accident [Venetsanos, A. G., Huld, T., Adams, P., & Bartzis, J. G. (2003). Source, dispersion and combustion modelling of an accidental release of hydrogen in an urban environment. Journal of Hazardous Materials, A105, 1–25]. In the cases where the hydrogen release is restricted, for example, by venting through a single PRD, the effects are relatively minor and localised close to the area of the flammable cloud. With increasing hydrogen storage pressure, the maximum energy available in a flammable cloud after a release increases, as do the predicted overpressures resulting from combustion. Even in the relatively confined environment considered, the effects on the combustion regime are closer to what would be expected in a more open environment, i.e. a slow deflagration should be expected.

Among the cases studied the most severe one was a rapid release of the entire hydrogen (40 kg) or natural gas (168 kg) storage system within the confines of a tunnel. In this case there was minimal difference between a release from a 20 MPa natural gas system or a 20 MPa hydrogen system, however, a similar release from a 35 MPa hydrogen system was significantly more severe and particularly in terms of predicted overpressures. The present study has also highlighted that the ignition point significantly affects the combustion regime in confined environments. The results have indicated that critical cases in tunnels may tend towards a fast deflagration, or where there are turbulence generating features, e.g. multiple obstacles, there is the possibility that the combustion regime could progress to a detonation.

When comparing the urban and tunnel environments, a similar release of hydrogen is significantly more severe in a tunnel, and the energy available in the flammable cloud is greater and remains for a longer period in tunnels. When comparing hydrogen and natural gas releases, for the cases and environments investigated and within the limits of the assumptions, it appears that hydrogen requires different mitigation measures in order that the potential effects are similar to those of natural gas in case of an accident. With respect to a PRD opening strategy, hydrogen storage systems should be designed to avoid simultaneous opening of all PRD, and that for the consequences of the released energy to be mitigated, either the number of PRDs opening should be limited or their vents to atmosphere should be restricted (the latter point would require validation by a comprehensive risk assessment).     

竖直分支管道泄爆开启压力对甲烷爆燃压力的影响研究

针对市政排污管网等典型受限空间内可燃气体爆燃风险,建立由水平管道和竖直分支管道构成的数值模型,研究竖直分支管道不同泄爆开启压力对甲烷爆燃压力的影响.研究结果表明:不同泄爆开启压力条件下,管道内存在爆燃压力积聚和泄放的双重效应;水平管道内各测点压力时程曲线均表现为先增大后减小而后出现亥姆霍兹振荡,随着与爆源距离的增加,初...     

不同形状受限空间内油气爆燃特性的实验研究

基于实验对4个不同形状的20L容器内的油气爆燃过程进行了研究,探讨了不同形状受限空间内爆炸压力荷载的变化和火焰行为的区别。结果表明:管道（短管和长管）的压力时序曲线较容积式受限空间（球形容器和立方体容器）的压力时序曲线更复杂,并且出现压力振荡;随着初始浓度的增加,超压值和平均升压速率均先增大后减小,在浓度为1.74%时达到最大值,此时,超压从大到小依次为:长管>短管>立方体>球形容器,平均升压速率从大到小依次为:短管>立方体>长管>球形容器;在爆燃初期,立方体中火焰行为为半球状层流火焰→扁平层流火焰,火焰速度先增大后减小,最大速度为12.5 m/s,长管中火焰行为为半球状层流火焰→拉伸指状火焰,火焰速度一直增大,最大速度为40 m/s。     

Experimental study on DDT for hydrogen–methane–air mixtures in tube with obstacles

An experimental study of flame propagation, acceleration and transition to detonation in stoichiometric hydrogen–methane–air mixtures in 6 m long tube filled with obstacles located at different configurations was performed. The initial conditions of the hydrogen–methane–air mixtures were 1 atm and 293 K. Four different cases of obstacle blockage ratio (BR) 0.7, 0.6, 0.5 and 0.4 and three cases of obstacle spacing were used. The wave propagation was monitored by piezoelectric pressure transducers PCB. Pressure transducers were located at different positions along the channel to collect data concerning DDT and detonation development. Tested mixtures were ignited by a weak electric spark at one end of the tube. Detonation cell sizes were measured using smoked foil technique and analyzed with Matlab image processing toolbox. As a result of the experiments the deflagration and detonation regimes and velocities of flame propagation in the obstructed tube were determined.     

Scale effects on hydrogen–air fast deflagrations and detonations in small obstructed channels

An experimental study of flame propagation, acceleration and transition to detonation in hydrogen–air mixture in 2-m-long rectangular cross-section channel filled with obstacles located at the bottom wall was performed. The initial conditions of the hydrogen–air mixture were 0.1 MPa and 293 K and stoichiometric composition (29.6% H₂ in air). The channel width was 0.11 m and blockage ratio was 0.5 in all experiments. The effect of channel geometrical scale on flame propagation was studied by using four channel heights H of 0.01, 0.02, 0.04, and 0.08 m. In each case, the obstacle height was equal to H/2 and the obstacle spacing was 2H.

The propagation of flame and pressure waves was monitored by four pressure transducers and four ion probes. The pairs of transducers and probes were placed at various locations along the channel in order to get information about the progress of the phenomena along the channel.

As a result of the experiments, the deflagration and detonation regimes and velocities of flame propagation in the obstructed channel were established.     

Differences in physical properties and CO2 gasification reactivity between coal char and petroleum coke

This paper mainly investigated the physical properties and gasification reactivity of coal char and petroleum coke, separately at the high temperature pyrolysis (950–1400 °C) with slow heating rate and pyrolysis pressure of the atmospheric pressure and at the pressurized pyrolysis (the atmospheric pressure to 3 MPa) with rapid heating rate and the pyrolysis temperature of 950 °C. Some significant differences in those between coal chars and petroleum coke were found. The high temperature pyrolysis caused more easily the graphitization of petroleum coke than that of coal char, especially in the higher temperature range. The increasing pyrolysis temperature resulted in the decrease of surface areas of coal char and the increase of surface areas of petroleum coke. As the pyrolysis pressure was elevated from the atmospheric pressure to 3 MPa, surface areas of petroleum coke initially increased and then decreased, while those of coal chars presented an opposite tendency. The increasing pyrolysis temperature was adverse to the gasification activity of coal chars and was favorable for the gasification activity of petroleum coke. Also, the effects of the pyrolysis pressure on the gasification activity of coal char and petroleum coke were significantly different. The gasification activity of petroleum coke was obviously lower than that of coal chars, and even lower than that of the natural graphite.     

Electrostatic spark ignition of sensitive dust clouds of MIE<1 mJ

Accidental electrostatic sparks in industrial plant producing/handling powders/dusts occur whenever a non-earthed electrically conducting object has been charged tribo-electrically to a high voltage and suddenly discharges its energy to earth via an air gap of appropriate length. When assessing the electrostatic spark ignition hazard in an industrial plant, the parameters of prime concern are the capacitances C of electrically conducting plant items that may become charged tribo-electrically, the voltages U to which they may become charged, and the minimum electric spark ignition energies (MIE) of the dust clouds of concern. Whenever , there is a possibility of accidental electrostatic spark ignition.

Current standard apparatuses for determining MIE of dust clouds have a lower spark energy limit of 2–3 mJ. In an investigation by the present authors, discussed in detail elsewhere, a new spark generator capable of producing synchronized capacitive sparks of energies down to the order of 0.01 mJ was developed and used for testing a selection of ignition-sensitive powders for MIE. Several of the MIEs found were 1–2 orders of magnitude lower than the lower energy limit of current standard test apparatus. Other experiments by the present authors, also reported elsewhere, have shown that quite low MIEs can be found for some dusts even with a less optimal synchronization mechanism, which may occur accidentally in practice.

The main object of the present paper is to discuss possible practical concerns arising from the finding that clouds in air of some dusts can have very low MIEs. In such cases, one may have to pay attention to even minor C values, i.e. minor plant items. Alternatively, with larger C values, even quite low voltages may give rise to hazardous spark discharges.

However, some types of fine metal powders of low MIEs will quite readily form electrically conductive layers on the solid surfaces with which they make contact. Hence, electrostatic spark ignition inside process equipment containing such dusts may be less probable than in the case of process equipment containing non-conducting dusts of correspondingly low MIEs.

There may be a need for a new standard test method for determination of MIEs of dust clouds in the <1 mJ range.