Are micro reactors inherently safe? An investigation of gas phase explosion propagation limits on ethene mixtures

A method for the determination of safety properties for micro reactors and micro structured components is presented. Micro structured reactors are not inherently safe but the range of safe operating conditions of micro reactors are extended since the explosion region is reduced. The λ/3 rule was demonstrated to be applicable to micro scale tubes for stoichiometric mixtures of ethane–oxygen and ethane–nitrous oxide. Furthermore first results from an investigation concerning detonation propagation through a micro reactor of non-ideal geometry are shown. Initial pressure investigated is ranging from low pressure up to 100 kPa.     

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.     

Explosibility of cork dust in methane/air mixtures

Explosibility studies of hybrid methane/air/cork dust mixtures were carried out in a near-spherical 22.7 L explosibility test chamber, using 2500 J pyrotechnic ignitors. The suspension dust burned as methane/air/dust clouds and the uniformity of the cork dust dispersion inside the chamber was evaluated through optical dust probes and during the explosion the pressure and the temperature evolution inside the reactor were measured. Tested dust particles had mass median diameter of 71.3 μm and the covered dust cloud concentration was up to 550 g/m³. Measured explosions parameters included minimum explosion concentration, maximum explosion pressures and maximum rate of pressure rise. The cork dust explosion behavior in hybrid methane/air mixtures was studied for atmospheres with 1.98 and 3.5% (v/v) of methane. The effect of methane content on the explosions characteristic parameters was evaluated. The conclusion is that the risk and explosion danger rises with the increase of methane concentration characterized by the reduction of the minimum dust explosion concentration, as methane content increases in the atmosphere. The maximum explosion pressure is not very much sensitive to the methane content and only for the system with 3.5% (v/v) of methane it was observed an increase of maximum rate of pressure rise, when compared with the value obtained for the air/dust system.     

Propagation of ethylene–air flames in closed cylindrical vessels with asymmetrical ignition

A study of explosions in several elongated cylindrical vessels with length to diameter L/D = 2.4–20.7 and ignition at vessel's bottom is reported. Ethylene–air mixtures with variable concentration between 3.0 and 10.0 vol% and pressures between 0.30 and 1.80 bara were experimentally investigated at ambient initial temperature. For the whole range of ethylene concentration, several characteristic stages of flame propagation were observed. The height and rate of pressure rise in these stages were found to depend on ethylene concentration, on volume and asymmetry ratio L/D of each vessel. High rates of pressure rise were found in the early stage; in later stages lower rates of pressure rise were observed due to the increase of heat losses. The peak explosion pressures and the maximum rates of pressure rise differ strongly from those measured in centrally ignited explosions, in all examined vessels. In elongated vessels, smooth p(t) records have been obtained for the explosions of lean C₂H₄–air mixtures. In stoichiometric and rich mixtures, pressure oscillations appear even at initial pressures below ambient, resulting in significant overpressures as compared to compact vessels. In the stoichiometric mixture, the frequency of the oscillations was close to the fundamental characteristic frequency of the tube.     

Effect of spark duration on explosion parameters of methane/air mixtures in closed vessels

The paper outlines an experimental study on influence of the spark duration and the vessel volume on explosion parameters of premixed methane–air mixtures in the closed explosion vessels. The main findings from these experiments are: For the weaker ignition the spark durations in the range from 6.5 μs to 40.6 μs had little impact on explosion parameters for premixed methane–air mixtures in the 5 L vessel or 20 L vessel; For the same ignitions and volume fractions of methane in air the explosion pressures and the flame temperatures in both vessels of 5 L and 20 L were approximately the same, but the rates of pressure rises in both vessels of 5 L and 20 L were different; The explosion indexes obtained from the measured pressure time histories for both vessels of 5 L and 20 L were approximately equal; For the weaker ignition with the fixed spark duration 45 μs the ignition energies in the range from 54 mJ to 430 mJ had little impact on the explosion parameters; For the same ignition and the volume fractions of methane in air, the vessel volumes had a significant impact on the flame temperatures near the vessel wall; The flame temperatures near the vessel wall decreased as the vessel volumes increased.     

Influence of the ignition source location on the determination of the explosion pressure at elevated initial pressures

Explosion pressures are determined for rich methane–air mixtures at initial pressures up to 30 bar and at ambient temperature. The experiments are performed in a closed spherical vessel with an internal diameter of 20 cm. Four different igniter positions were used along the vertical axis of the spherical vessel, namely at 1, 6, 11 and 18 cm from the bottom of the vessel. At high initial pressures and central ignition a sharp decrease in explosion pressures is found upon enriching the mixture, leading to a concentration range with seemingly low explosion pressures. It is found that lowering the ignition source substantially increases the explosion pressure for mixtures inside this concentration range, thereby implying that central ignition is unsuitable to determine the explosion pressure for mixtures approaching the flammability limits.     

Fire and Explosion Characteristics of 3-Methyl Pyridine at 270°C with High Oxygen Concentrations

The mixture of 3-methyl pyridine (3-picoline) and steam is used in the production of vitamin B3 in the gas phase. The aim of this study was to investigate the influence of inert steam (H₂O) on the flammability characteristics of 3-picoline in the manufacturing process. Four practical vapour mixing ratios of 3-picoline/steam mixtures, 5, 10, 30 and 100 vol% 3-picoline, were selected in this study. A series of flammability tests were employed for determining their fire and explosion characteristics. Fire tests H₂O: 3-picoline 5,10, 30 and 100 vol% were carried out in a 20-L-Apparatus under simulated conditions of 760 mmHg, 270°C, together with high oxygen concentrations (42 and 21 vol%) used in the real process.The experimental results showed that the safety-related parameters and flammability hazard degrees were all able to be significantly reduced while substantial amount of steam was infused into the 3-picoline/steam system. While the steam proportion was up to 97 vol%, 3-picoline/steam would be non-flammable. As a result, dosing steam to the process is one of the effective methods to prevent the relevant processes from incurring fire and explosion hazards, not to mention its economical benefit.     

Explosion regions of 1,3-dioxolane/nitrous oxide and 1,3-dioxolane/air with different inert gases - Experimental data and numerical modelling

In this study, experimental determination and modelling investigations for the explosion regions of 1,3-dioxolane/inert gas/N₂O and 1,3-dioxolane/inert gas/air mixtures were carried out and compared. The experimental measurements were carried out at 338 K and atmospheric pressure according to EN1839 method T using the inert gases N₂, CO₂, He and Ar. The results showed that the ratio of the lower explosion limit in N₂O (LEL_N2O) to the lower explosion limit in air (LEL_air) is 0.52 and the ratio of the maximum oxygen content in air (MOC_air) to the limiting oxidizer fraction in nitrous oxide (LOF_N2O) is 0.36 ± 0.02 independent of the inert gas. When comparing the inert gas amount at the apex based on the pure oxidizing component, which is O₂ in case of air, N₂O-containing mixtures need less inert gas to reach the limiting oxidizer quantity whereas the efficiency of inert gases is in the same order. The coefficients of nitrogen equivalency however were found to differ to some extent. The explosion regions of 1,3-dioxolane/inert gas/oxidizer mixtures were modelled using the calculated adiabatic flame temperature profile (CAFTP) method as well as corrected adiabatic flame temperatures. The results indicate good agreement with experimental data for CO₂, N₂ and Ar- containing mixtures. The noticeable deviations that occur when He is the inert gas are due to the lacking transport data of that mixture.     

Experimental analysis of gas explosions at non-atmospheric initial conditions in cylindrical vessel

Accidental gas explosions in industrial equipment are seldom initiated at atmospheric conditions. Furthermore, fuel–air mixtures are generally turbulent due to rotating parts or flows. Despite these considerations, few studies have been devoted to the analysis of explosion properties at conditions of temperature and pressure different from ambient and in the presence of turbulence; therefore, experiments are still needed, even at lab-scale, e.g. for the design of mitigation system as venting devices.In this work, experimental explosion tests have been performed in 5 l, cylindrical tank reactor with stoichiometric methane–air mixtures at initial pressure and temperature up to 600 kPa and 400 K, centrally ignited or top ignited, and with the effect of initial turbulence level by varying the velocity of the mechanical stirrer.     

Experimental study on vented gas explosion in a cylindrical vessel with a vent duct

A study of vented explosions in a length over diameter (L/D) of 2 in cylindrical vessel connecting with a vent duct (L/D = 7) is reported. The influence of vent burst pressure and ignition locations on the maximum overpressure and flame speeds at constant vent coefficient, K of 16.4 were investigated to elucidate how these parameters affect the severity of a vented explosion. Propane and methane/air mixtures were studied with equivalence ratio, Φ ranges from 0.8 to 1.6. It is demonstrated that end ignition exhibited higher maximum overpressures and flame speeds in comparison to central ignition, contrary to what is reported in literature. There was a large acceleration of the flame toward the duct due to the development of cellular flames and end ignition demonstrated to have higher flame speeds prior to entry into the vent due to the larger flame distance. The higher vent flow velocities and subsequent flame speeds were responsible for the higher overpressures obtained. Rich mixtures for propane/air mixtures at Φ = 1.35 had the greatest flame acceleration and the highest overpressures. In addition, the results showed that Bartknecht's gas explosion venting correlation is grossly overestimated the overpressure for K = 16.4 and thus, misleading the impact of the vent burst pressure.     

Electrostatic ignition of sensitive flammable mixtures: Is charge generation due to bubble bursting in aqueous solutions a credible hazard?

Experiments have been conducted to gain insight into the credibility of sparging aqueous solutions as an electrostatic ignition hazard for sensitive hydrogen/air or fuel/oxygen mixtures (Minimum Ignition Energies of ∼0.017 mJ and ∼0.002 mJ, respectively, compared to ∼0.25 mJ for hydrocarbon/air mixtures). Tests performed in a 0.5 m³ ullage produced electric field strengths between 125 and 560 V m⁻¹ for air flows of 5–60 l min⁻¹, respectively, comprised of 2–4 mm diameter bubbles. Field strength can be related to the space charge and fitting to an exponential accumulation curve enabled the charge generation rate from the air flows to be estimated. This was observed to be directly proportional to the air flow and its magnitude was consistent with literature data for bubble bursts. The charge accumulation observed at laboratory scale would not be a cause for concern. On the basis of a simple model, the charge accumulation in a 27 m³ ullage was predicted for a range of air flows. It is apparent from such calculations that ignition of hydrocarbon/air mixtures would not be expected. However, it would seem possible that field strengths might be sufficient to cause a risk of incendive spark or corona discharges in moderately sized vessels with sensitive flammable mixtures.     

Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

Experiments on the influence of pre-ignition turbulence on vented gas and dust explosions

Experiments were performed on the influence of pre-ignition turbulence on the course of vented gas and dust explosions. A vertical cylindrical explosion chamber of approximately 100 l volume and a length-to-diameter ratio (l/d) of 4.7 consisting of a steel bottom segment and three glass sections connected by steel flanges was used to perform the experiments. Sixteen small fans evenly distributed within the chamber produced turbulent fluctuations from 0 to 0.45 m/s. A Laser-Doppler-anemometer (LDA) was used to measure the flow and turbulence fields. During the experiments the pressure and in the case of dust explosions the dust concentration were measured. In addition, the flame propagation was observed by a high-speed video camera. A propane/nitrogen/oxygen mixture was used for the gas explosion experiments, while the dust explosions were produced by a cornstarch/air mixture.It turned out that the reduced explosion pressure increased with increasing turbulence intensity. This effect was most pronounced for small vents with low activation pressures, e.g. for bursting disks made from polyethylene foil. In this case, the overpressure at an initial turbulence of 0.45 m/s was twice that for zero initial turbulence.     

Electrowinning studies for metallic zinc production from double leached Waelz oxide

Waelz oxide is a zinc and lead concentrate pyrometallurgically derived from electric arc furnace dust. There are clear incentives to leaching and purify this oxide to produce liquors that can be electrowinned to obtain recycled metallic zinc. This study is focused on this electrolytic zinc production from previously obtained sulphuric liquor. This liquor was obtained from double leached Waelz oxide (DLWO) throughout a hydrometallurgical process. The electrolytic liquor, after the corresponding leaching and purification stages, contains around 49 kg/m³. This liquor was fed to an electrowinning process where platinum or lead anodes and aluminium cathodes were used. After optimizing the different electrowinning critical parameters, and working at these optimal conditions, almost 88 secondary zinc kg were precipitated per each initial DLWO tonne in one-through process. The zinc purity was higher than 99.5%. After some mass balance calculations, it can be concluded that, optimizing the process configuration through internal recycling, around 210 Zn kg/DLWO t with purity near to 100% could be achieved.     

The explosion overpressure field and flame propagation of methane/air and methane/coal dust/air mixtures

The explosion of the methane/air mixture and the methane/coal dust/air mixture under 40 J center spark ignition condition was experimentally studied in a large-scale system of 10 m³ vessel. Five pressure sensors were arranged in space with different distances from the ignition point. A high-speed camera system was used to record the growth of the flame. The maximum overpressure of the methane/air mixture appeared at 0.75 m away from the ignition point; the thickness of the flame was about 10 mm and the propagation speed of the flame fluctuated around 2.5 m/s with the methane concentration of 9.5%. The maximum overpressure of the methane/coal dust/air mixture appeared at 0.5 m. The flame had a structure of three concentric zones from outside were the red zone, the yellow illuminating zone and the bright white illuminating zone respectively; the thickness and the propagation speed of the flame increased gradually, the thickness of red zone and yellow illuminating zone reached 3.5 cm and 1 cm, the speed reached 9.2 m/s at 28 ms.     

Experimental studies of ignition and explosions in cyclohexane liquid under oxygen oxidation conditions

The safe operation of hydrocarbon liquid-phase oxidation by air or oxygen requires the knowledge on the flammability of hydrocarbon/oxygen mixtures in both the vapor space and vapor bubbles. The latter is of particular importance in situation where pure oxygen is used as the oxidant as most bubbles are expected to be flammable and explosive. New experimental findings are presented for ignition and explosion in cyclohexane liquid under oxygen oxidation conditions. A bubble column is constructed and fitted with multiple igniters. Experiments were performed at liquid temperatures between 373.15 and 423.15 K under various flow rates of pure oxygen. Two drastic different ignition and explosion behaviors were observed. The first is a typical bubble explosion from the direct ignition of the flammable bubbles in the liquid. The explosion occurs immediate following the ignition and do not produce significant energy that endanger the system. The other is a remote, delayed ignition and explosion in the vapor space that can produce significant overpressure and endanger the system. The explosion is attributed to the ignition of flammable vapor space by active free radicals from cyclohexyl hydroperoxide decomposition. A mechanism is proposed for the remote, delayed ignition to occur in the oxidation system. It is concluded that explosion in an oxidizing, bubbly liquid is not only a likely scenario but also a severe scenario, and cyclohexane oxidation should not be carried out directly with pure oxygen and without any inerting.     

Determination of explosion parameters of methane-air mixtures in the chamber of 40 dm3 at normal and elevated temperature

The experimental results of the measurements of the explosion pressure and rate of explosion pressure rise as a function of molar methane concentration in the mixture with air in the 40 dm³ explosion chamber are presented. The research was aimed at determination of the explosion limits, according to the EU Standard. The influence of initial temperature of the mixture (changing in the range of 293–473 K) on the fundamental explosion parameters was also investigated. The ignition source was an induction electrical spark of the power equal to approximately 10 W. It was stated, that the increase of initial temperature of the methane-air mixture causes a significant increase of the explosion range.     

Large scale high pressure jet fires involving natural gas and natural gas/hydrogen mixtures

A series of six large scale high pressure jet fires were conducted using natural gas and natural gas/hydrogen mixtures. Three tests involved natural gas and three involved a mixture of natural gas and hydrogen containing approximately 24% by volume hydrogen. For each fuel, the three tests involved horizontal releases from 20, 35 and 50 mm diameter holes at a gauge pressure of approximately 60 bar. During the experiments, the flame length and the incident radiation field produced around the fire were measured. The fires also engulfed a 1 m diameter horizontal pipe placed across the flow direction and about halfway along the flame. This pipe was instrumented to measure the heat fluxes to the pipe. The data obtained is compared with previous data obtained for various hydrocarbons at large scale.     

Explosions and deflagration-to-detonation transitions in epoxy propane/air mixtures

The explosion and deflagration-to-detonation transition (DDT) in epoxy propane (E.P.) vapor/air mixture clouds under weak ignition conditions has been studied in an experimental tube of diameter 199 mm and length 29.6 m. E.P. vapor clouds were formed by injecting liquid E.P. into the experimental tube and evaporating of the fine E.P. droplets. The dimension and the evaporating process of the E.P. droplet were measured and analyzed. The E.P. vapor/air mixture clouds were ignited by an electric spark with an ignition energy of 40 J. The characteristics and the stages of the DDT process in the E.P. vapor/air mixtures have been studied and analyzed. A self-sustained detonation wave formed, as was evident from the existence of a transverse wave and a cellular structure. Moreover, a retonation wave formed during the DDT process in the E.P. vapor/air mixture. The influence of the E.P. vapor concentration on the DDT process has been studied. The minimum E.P. vapor concentration for the occurrence of the DDT in the E.P. vapor/air mixture has been evaluated and the variation of DDT distance with E.P. vapor concentration has been analyzed.     

Investigation of affecting parameters on treating high-strength compost leachate in a hybrid EGSB and fixed-bed reactor followed by electrocoagulation–flotation process

In this research, treatability of high-load compost leachate in a hybrid expanded granular sludge bed (EGSB) and fixed-bed (FB) bioreactor followed by electrocoagulation–flotation (ECF) system was examined. The operational factors in EGSB–FB were influent chemical oxygen demand (COD), hydraulic retention time (HRT) and COD/nitrogen ratio (COD/N). And, their interactive effects on the efficiency of COD removal and biogas production rate (BPR) as responses were analyzed and correlated by response surface methodology (RSM). The optimum conditions of the hybrid EGSB–FB reactor were acquired at COD = 7800 mg/L, HRT = 35 h, COD/N = 70, in which COD removal efficiency was 83% and BPR 94 mL/h. The amount of confidence interval was 95%. COD (relevant coefficient = 9.8) and HRT (relevant coefficient = −24) were resulted respectively as the most effective parameters on COD removal and BPR. Yet, COD/N parameter imposed negative effect on COD removal and BPR in values less than about 100. The outcomes indicated that operated ECF as post-treatment in constant conditions (electrolysis time = 75 min, electrodes distance = 3 cm, voltage = 20 V) successfully satisfied discharge criteria in the most part of experimental domains.