Effects of N2 and CO2 on the flammability of 2,3,3,3-tetrafluoropropene at elevated temperatures

The flammability characteristics of refrigerants are affected by environmental factors, making them prone to flammability and explosion accidents in cooling systems. In this paper, the flammability characteristics of R1234yf–air mixtures with N₂ and CO₂ were investigated comparatively at temperatures between 20 and 50 °C at 80% relative humidity. The lower and upper flammability limits of R1234yf were measured. The limiting oxygen concentration (LOC), critical flammable ratio (CFR), and critical flammable concentration (CFC) of the R1234yf–air mixtures with inert gases were investigated. The paper developed a linear formula between the flammability limit of R1234yf and the temperature. The changes in CFC with different temperatures were negligible for R1234yf. Furthermore, the mixed refrigerant had both non-flammability and the lowest vapor pressure when the CFR of the R1234yf/CO₂ mixture was 2.9. The experimental results were used to propose a new prediction model to estimate the flammability limits of R1234yf. Finally, molecular simulation explained the effect of inert gases on the flammability of R1234yf from a microscopic point of view. The research aimed to provide valid evidence and data for preventing flammable and explosive refrigerant incidents.     

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.     

Prediction of flammability limits of fuel-air and fuel-air-inert mixtures from explosivity parameters in closed vessels

Flammability limits of fuel-air and fuel-air-inert gaseous mixtures, especially at non-atmospheric conditions, are essential properties required for establishing safety operating conditions for handling and processing flammable gases. For pure fuels, an important data pool exists, formed by the flammability limits of fuel-air and fuel-air-inert gaseous mixtures at ambient initial conditions measured by standard methods. Such methods can be used for experimental determination of flammability limits for multi-fuels mixed with air, with or without additives, under non-atmospheric conditions. Their use is however a time- and material-consuming process; in addition, the flammability limits obtained by various standard methods may be scattered as a result of different choices in the operating parameters, for each standard method. It appears that a preliminary estimation of the flammability limits for fuel-air and fuel-air-inert gaseous mixtures can minimize the effort of measuring them in specific initial conditions.The present paper describes a new method for estimating the flammability range of fuel-oxidizer gaseous mixtures based on measurements of explosivity properties e.g. the peak explosion pressure and maximum rate of pressure rise recorded during closed vessel laminar explosions of fuel-oxidizer mixtures far from limits. Data obtained for several hydrocarbon-air gaseous mixtures with or without inert gas addition are used to examine the accuracy of estimated flammability limits (LFL – the lower and UFL – the upper flammability limit) as well as of the Limiting Oxygen Concentration (LOC) and the Minimum Inert Concentration (MIC). The predictive ability of the proposed method is examined against the predictive ability of other recently described methods.     

Study of the explosion parameters of vapor–liquid diethyl ether/air mixtures

The knowledge of the vapor–liquid two-phase diethyl ether (DEE)/air mixtures (mist) on the explosion parameters was an important basis of accident prevention. Two sets of vapor–liquid two-phase DEE/air mixtures of various concentrations were obtained with Sauter mean diameters of 12.89 and 22.90 μm. Experiments were conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at an ignition energy of 40.32 J and at an initial room temperature and pressure of 21 °C and 0.10 MPa, respectively. The effects of the concentration and particle size of DEE on the explosion pressure, the explosion temperature, and the lower and upper flammability limits were analyzed. Finally, a series of experiments was conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at various ignition energies. The minimum ignition energies were determined, and the results were discussed. The results were also compared against our previous work on the explosion characteristics of vapor–liquid two-phase n-hexane/air mixtures.     

Influence of concentration distribution of hydrogen in air on measured flammability limits

There is a clear difference between exiting data on the measured flammability limits of hydrogen-air mixture. The non-uniformity of concentration distribution of hydrogen in air is a contributor to deviations of the upper flammability limit (UFL) and the lower flammability limit (LFL) measured in different experiments. This paper presents a numerical model to simulate the gas mixing process from start to stability, to predict the concentration distribution, and to research the influence of concentration distribution of hydrogen in air on measured UFLs and LFLs. The commercial software package Fluent was used to carry out the numerical simulation for the concentration distribution of hydrogen in air in the vessels with length-to-diameter ratios (L: D) of 1:1, 3:1, 5:1 and 7:1 respectively. Based on the numerical simulation and analysis, the influence of concentration distribution on measured flammability limits was demonstrated for hydrogen in air in the vessel. It is found that the deviations of measured flammability limits of hydrogen in air are the minimum in the vessel with length-to-diameter ratio of 1:1, and augment with the augmentation of vessel length-to-diameter ratio. Moreover, it is presented that the deviations of measured flammability limits of hydrogen in the center of the vessel are lower than that in the top and the bottom.     

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 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.     

Experimental measurement and numerical analysis of binary hydrocarbon mixture flammability limits

The flammability limits of binary hydrocarbon mixtures in air were measured in a combustion apparatus using an innovative method developed for this apparatus. The experimental results were obtained at standard conditions (room temperature and ambient atmospheric pressure) with upward flame propagation. The experimentally determined flammability limits for pure hydrocarbons (methane and ethylene) were compared with existing data reported in the literature. Le Chatelier's Law was fit to all experimental data to obtain LFLs and UFLs for various two-component combinations of saturated and unsaturated hydrocarbons (methane, ethylene, acetylene, propane, propylene, and n-butane). A modification of this law was used if experimental observations showed large deviations from Le Chatelier's predictions. Also, experimentally measured flammability limit data of the binary hydrocarbon mixtures were analytically related to the stoichiometric concentrations.     

Flammability limits of binary mixtures of dimethyl ether with five diluent gases

Flammability limits of binary mixtures of dimethyl ether with five kinds of diluent gases were measured by ASHRAE method at room temperature. The five diluent gases are nitrogen, carbon dioxide, chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The experimental results were correlated with the extended Le Chatelier's formula. It was found that the experimental results were well reproduced by the formula. In addition, flammability limits of binary mixtures of dimethyl ether with nitrogen and carbon dioxide were compared with the estimated values based on the adiabatic flame temperature method. The experimental results were found to be in satisfactory agreement with the estimated values.     

Theoretical and experimental study of the inhibition and inert effect of HFC125, HFC227ea and HFC13I1 on the flammability of HFC32

HFC32 is a potential alternative refrigerant with excellent thermal performance, but the flammability is a main obstacle for its applications. The group contribution method is utilized to analyze the inhibition efficiency of nonflammable refrigerants in binary mixtures. Furthermore, a novel equation of predicting the minimum inerting concentration of nonflammable refrigerants has been proposed by analyzing the variation of the flame propagation velocity and the flammable refrigerant concentration. Experimental studies of the explosion limits of HFC125/HFC32, HFC227ea/HFC32 and HFC13I1/HFC32 were carried out and the ranges of explosion limits were obtained. At the same time, the relationship between the maximum charge of the flammable refrigerants and lower flammability limit (LFL) was analyzed. The result demonstrates that the proposed novel theoretical equation can effectively predict the minimum inerting concentration of nonflammable refrigerants to flammable refrigerants, and the theoretical results have significance on the security application of the binary mixtures.     

Study of the severity of hybrid mixture explosions and comparison to pure dust-air and vapour-air explosions

The explosion behaviour of heterogeneous/homogeneous fuel-air (hybrid) mixtures is here analysed and compared to the explosion features of heterogeneous fuel-air and homogeneous fuel-air mixtures separately.Experiments are performed to measure the pressure history, deflagration index and flammability limits of nicotinic acid/acetone-air mixtures in a standard 20 L Siwek bomb adapted to vapour-air mixtures. Literature data are also used for comparison.The explosion tests performed on gas-air mixtures in the same conditions as explosion tests of dust-air mixtures, show that the increase in explosion severity of dust/gas-air mixtures has to be addressed to the role of initial level of turbulence prior to ignition.At a fixed value of the equivalence ratio, by substituting the dust to the flammable gas in a dust/gas-air mixture the explosion severity decreases. Furthermore, the most severe conditions of dust-gas/air mixtures is found during explosion of gas-air mixture at stoichiometric concentration.     

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.     

Numerical studies on minimum ignition energies in methane/air and iso-octane/air mixtures

In this study, the dependence of minimum ignition energies (MIE) on ignition geometry, ignition source radius and mixture composition is investigated numerically for methane/air and iso-octane/air mixtures. Methane and iso-octane are both important hydrocarbon fuels, but differ strongly with respect to their Lewis numbers. Lean iso-octane air mixtures have particularly large Lewis numbers. The results show that within the flammability limits, the MIE for both mixtures stays almost constant, and increases rapidly at the limits. The MIEs for both fuels are also similar within the flammability limits. Furthermore, the MIEs of iso-octane/air mixtures with a small spherical ignition source increase rapidly for lean mixtures. Here the Lewis number is above unity, and thus, the flame may quench because of flame curvature effects. The observations show a distinct difference between ignition and flame propagation for iso-octane. The minimum energy required for initiating a successful flame propagation can be considerably higher than that required for initiating an ignition in the ignition volume. For iso-octane with a small spherical ignition source, this effect was observed at all equivalence ratios. For iso-octane with cylindrical ignition sources, the phenomenon appeared at lower equivalence ratios only, where the mixture's Lewis number is large. For methane fuel, the effect was negligible. The results highlight the significance of molecular transport properties on the decision whether or not an ignitable mixture can evolve into a propagating flame.     

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.     

Determination of the maximum effective burning velocity of dust–air mixtures in constant volume combustion

The reactivity of a combustible dust cloud is traditionally characterized by the so-called K_St value, defined as the maximum rate of pressure rise measured in constant volume explosion vessels, multiplied with the cube root of the vessel volume. The present paper explores the use of an alternative parameter, called the maximum effective burning velocity (u_eff,max), which also is derived from pressure–time histories obtained in constant volume explosion experiments. The proposed parameter describes the reactivity of fuel–air mixtures as a function of the dispersion-induced turbulence intensity. Procedures for estimating u_eff,max from tests in both spherical and cylindrical explosion vessels are outlined, and examples of calculated values for various fuel–air mixtures in closed vessels of different sizes and shapes are presented. Tested fuels include a mixture of 7.5% methane in air, and suspensions of 500 g/m³ cornstarch in air and 500 g/m³ coal dust in air. Three different test vessels have been used: a 20-l spherical vessel and two cylindrical vessels, 7 and 22 l. The results show that the estimated maximum effective burning velocities are less apparatus dependent than the corresponding K_St values.     

Safety parameters for oxygen-enriched flames

The utilization of low-quality gaseous fuel from biomass gasification and the abundance of oxygen-rich streams obtained as a by-product of nitrogen-air separation by membrane technology has incentivized the development of sustainable oxygen-enriched combustion technologies in the last decades. However, a dearth of experimental and numerical analysis addressing the reactivity and safety aspects of these mixtures at initial low temperatures can be observed in the current literature.In this work, the heat flux burner was adopted for the measurement of the laminar burning velocity of methane in oxygen enriched air at different equivalence ratios. Results were compared with numerical data obtained by means of detailed kinetic mechanisms developed at the University of Bologna and the Gas Research Institute (GriMech3.0). Simplified correlations for the estimation of the laminar burning velocity with respect to the oxygen content at any equivalence ratio were developed, tested and evaluated.An elemental reaction-based function was found appropriate for the estimation of the overall reactivity of the investigated mixtures. Besides, numerical analyses were performed to characterize the flame structures in terms of temperature and product distribution under several initial conditions. These results gave further insights into the reaction mechanisms of gaseous fuels in the case of oxygen-enriched air, highlighting potential bottlenecks for kinetic model refinements. Eventually, relevant safety parameters were estimated, in particular the flammability range of the fuel/oxidant mixture, in terms of lower and upper flammability limits.     

Effects of initial temperature and pressure on explosion characteristics of propane–diluent–air mixtures

The explosion characteristics of propane–diluent–air mixtures under various temperatures and pressures were investigated using a 20-L apparatus. The explosion limits of propane diluted with nitrogen or carbon dioxide were measured at high temperatures from 25 to 120 °C. The results showed that the upper explosion limit (UEL) increased, and the lower explosion limit (LEL) decreased with the rising temperature. The explosion limits of propane diluted with nitrogen or carbon dioxide were also measured at high pressures from 0.10 to 0.16 MPa. The results showed that the UEL increased, and the LEL almost remainedunchanged along with increased pressure. Under the same initial operating conditions, the concentration of nitrogen required to reach the minimum inerting concentration (MIC) point was higher than the concentration of carbon dioxide. Finally, the study investigated the limiting oxygen concentration (LOC) of propane under various initial temperatures, initial pressures, and inert gases. The LOC of propane decreased approximately linearly with increased temperature or pressure, and the LOC of propane dilution with carbon dioxide was greater than dilution with nitrogen from 25 to 120 °C or from 0.10 to 0.16 MPa, which indicated that the dilution effect of carbon dioxide was better than that of nitrogen.     

An investigation of flammability limits of gaseous mixtures at reduced pressures

An experimental investigation of flammability limits of hydrogen, methane and propane in air and oxygen at reduced pressures was carried out. A slow influence of sizes of an experimental vessel of a diameter higher than 125 mm on the flammability limits was revealed, but an influence of a type of an oxidizer (air or oxygen) and an ignition energy is significant. Critical values of an initial pressure for a possibility of a flame propagation were determined. The limiting values of the ignition energy were determined, for which an elevation of this parameter does not influence the critical pressure and the flammability region. A qualitative interpretation of obtained experimental results is given, which is based on a peculiarities of a flame initiation.     

Experimental research on the flammability characteristics of several binary blends consisting of 1-Chloro-1,1-difluoroethane and extinguishing agents

1-Chloro-1,1-difluoroethane (R142b) can be used as the refrigerant, foaming agent and ORC (Organic Rankine Cycle) fluid. R142b was described as one of the interim substitutes in the Montreal Protocol (signed in 1987), and allowed to be used in developing countries until 2040. However the production and consumption of R142b were required to be frozen this year on the average data of 2009 and 2010 according to its latest amendment (signed in 2007). Binary alternatives R245fa/R142b, R227ea/R142b, R600a/R142b and R134a/R142b are possible substitutes in the initial transition period of frozen and phase-out R142b for the reason of pressure approach, which may be welcomed by the countries with wide use of R142b considering the technology and cost. This paper contributes to the flammability of these binary mixtures experimentally by using a self-made test rig built on the ground of Chinese National Standard. Not only the flammable limits of blends were studied, but also the related flame images were presented and analyzed. In addition, the flame suppression efficiencies of R245fa, R227ea and R134a have been compared and the lower flammable limits of R600a/R142b has been estimated and tested at different ratios. The presented work is beneficial to environmental protection.     

Fast flame speeds and rates of pressure rise in the initial period of gas explosions in large L/D cylindrical enclosures

Flame speeds and rates of pressure rise for gaseous explosions in a 76 mm diameter closed cylindrical vessel of large length to diameter ratio (L/D = 21.6), were quantitatively investigated. Methane, propane, ethylene and hydrogen mixtures with air were studied across their respective flammability ranges. Ignition was affected at one end of the vessel. Very fast flame speeds corresponding to high rates of pressure rise were measured in the initial 5–10% of the total explosion time. During this period 20–35% of the maximum explosion pressure was produced, and over half of the flame propagation distance was completed. Previous work has concentrated on the later stages of this type of explosion; the development of tulip flames, pressure wave effects and transition to turbulence. The initial fast phase is very important and should dominate considerations in pressure relief vent design for vessels of large L/D.