Experimental study on the influence of flame retardants on the flammability of R1234yf

As an alternative refrigerant, R1234yf shows great environmental friendliness. However, the flammability has a negative impact on its use and promotion. To lower the combustible risk, it's a proper way to mix with nonflammable refrigerants in applications, but the research on the flammability of these blends is still limited. Therefore, the influence of three typical nonflammable refrigerants CO₂, R1336mzz(E) and R1233zd(E) as flame retardants on the flammability of R1234yf was experimentally studied in this paper. With the measurements of flammable limits of R1234yf/CO₂, R1234yf/R1336mzz(E) and R1234yf/R1233zd(E) at different concentrations, the parameters of regression equations for their flammable limits were obtained. The critical suppression concentrations of retardant were determined as 0.575, 0.35 and 0.6, respectively. The results showed that their suppression abilities could be ranked as R1336mzz(E)>CO₂>R1233zd(E). Then the inhibition mechanisms were analyzed, and the differences in flame colors at flammable limits were compared. With the establishment of estimation model for calculating critical suppression concentrations of ternary blends, the critical suppression lines of CO₂/R1234yf/R1336mzz(E) and CO₂/R1234yf/R1233zd(E) were obtained, by which the nonflammable zones of them were preliminarily determined. The results will provide practical guidance for the applications utilizing R1234yf and its blends in safety.     

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.     

Effect of initial temperature on explosion characteristics of 2, 3, 3, 3–Tetrafluoropropene

The flammability of refrigerants is a major cause of refrigerant explosion incidents. Studying the explosion characteristics of refrigerants at different initial temperatures can provide significant benefits for solving the safety problems of refrigerants under actual working conditions. This paper studied the effects of the initial temperature and refrigerant concentration on the explosion characteristics of refrigerant 2, 3, 3, 3-tetrafluoropropene (R1234yf) at 0.1 MPa. The curves of explosion characteristics with different initial temperature revealed the same variation trend ranged from 25 °C to 115 °C. Specifically, as the refrigerant concentration was raised, the peak overpressure, the maximum rate of pressure rise, and laminar burning velocity increased initially and decreased afterwards, along with maximum values at the refrigerant concentration of 7.6%. When the refrigerant concentration was 7.6%, the peak overpressure declined exponentially with the initial temperature rise, while the maximum rate of pressure rise increased linearly. The laminar burning velocity calculated from the spherical expansion method indicated that the flame propagation was gradually accelerated by the increase of initial temperature, which coincided with the change of the maximum rate of pressure rise. Meanwhile, experiments and CHEMKIN simulation results demonstrated the effects of elevated temperature from 20 °C to 50 °C on the explosion limits of R1234yf. The lower explosion limit reduced and the upper explosion limit increased with rising initial temperature. In general, R1234yf exhibited moderate combustion and lower explosion risk, compared with traditional refrigerants.     

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.     

Turbulent deflagrations of mildly flammable refrigerant-air mixtures

With current concerns around global climate change, new hydrofluorocarbons with low Global Warming Potential (GWP) are being evaluated as alternative refrigerants. These alternative refrigerants, however, may be mildly flammable (as defined by the A2L safety group classification) and pose safety concerns for the heating, ventilation, air conditioning, and refrigeration (HVAC/R) industry. Consequently, careful assessments of different flammability characteristics and risks for these refrigerants are essential for their safe use in actual applications. In this study, deflagration propagation measurements for different mildly flammable refrigerants, including difluoromethane (R-32) and 2,3,3,3-tetrafluoropropene (R-1234yf), were undertaken in different geometries including a 9.1-m long conduit test rig and a closed cubical 12.5 m³ volume. Different tests were conducted for full volume deflagrations as well as with and without obstructions. Turbulent deflagration speeds for well-mixed, refrigerant-air mixtures have been shown to be orders of magnitude larger than their corresponding laminar flame speed values that are used in classifying flammable refrigerants in safety standards. Testing has also quantified the resulting severity as measured by the event overpressure which was shown to worsen with increased congestion or confinement as a consequence of increased induced turbulence. This work illustrates the importance for severity evaluations for actual large-scale or congested geometries of concern in practical applications. Even for mildly flammable refrigerants characterized by laminar flame speeds <2 cm/s, which is lower than the 10 cm/s limit for A2L refrigerants, relatively fast deflagrations can be generated for very congested geometries where downstream turbulence is generated as the flame front passes over obstacles in these situations.     

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.     

可燃制冷剂泄漏及爆炸危害评价的研究

建立了计算可燃工质泄漏后在房间内可燃工质浓度变化的模型。计算结果表明,小型空调器可燃工质泄漏引发的爆炸隐患仅局限于空调系统附近的局部区域内。用压力－冲量准则,对可燃工质泄漏产生的最大爆炸当量、危害范围与危害等级进行分析研究。结果表明,使用充装量很小的可燃制冷剂,泄漏产生爆炸的危险性很小,火灾隐患是主要的。     

Suppression of flame propagation in a long duct by inertia isolation with inert gases

Experimental studies were done with a small pipe with a diameter of 0.043 m and a large pipe with a diameter of 0.49 m to demonstrate the flame propagation suppression with inertia isolation in a long duct. Tests were carried in an ignition section containing propylene/air mixture near stoichiometric concentration and generating a peak flame propagation speed of approximately 100 m/s. The ignition section is connected to a section filled with an inert gas, another section with flammable mixtures, and finally a sufficiently long, ambient section to accommodate flame propagation. The critical length of the inert gas section required for successful suppression of flame from the igniting the flammable section is found to be 0.6 m for CO₂ and 0.9 m for N₂ in the large pipe and 0.2 m for CO₂ and 0.3 m for N₂ in the small pipe. Additional tests with a 3 m of ignition section and peak flame propagation speed of 225 m/s showed that the critical length for successful suppression by CO₂ is only increased slightly to 0.9 m, confirming that the suppression is a result of inertia isolation rather than inert gas dilution. Finally, application of the results in responding to large-scale leak into a long, underground duct is discussed.     

可燃制冷剂空调用开关元件点燃危险及防爆试验分析

随着全球范围对环境问题的日益重视,R290,R32等新型制冷剂因优良的环保性能和节能效果被广泛应用于空调行业,但其属于IIA级爆炸性气体,为了进一步分析其运行过程中的防爆安全性能。通过文献数据和测试分析,可燃制冷剂空调电气元件的点燃源主要来自其工作过程中产生的电气火花。其中空调开关元件最容易产生电火花、电弧,且通过试验验证这些火花或电弧能点爆（6.5±0.5）%乙烯/空气混合物。综合IEC 60335-2-40,GB 4706.32标准要求和空调开关元件的结构特征,分析确定其应符合“nC”型防爆技术要求,并能通过“nC”型爆炸试验。针对开关元件结构尺寸小、存在爆炸试验中爆炸性混合气体多次置换和负载通、断电操作的难点问题,提出一套合理可行的爆炸试验实施方案,并通过测试应用得到验证。     

Experimental evaluation of the possibility of ignition and flame propagation in accumulated difluoromethane (R32) from a kerosene cigarette lighter

The possibility of ignition and flame propagation in accumulated difluoromethane (CH₂F₂, R32) was examined experimentally, simulating a situation in which a service operative uses a kerosene lighter for smoking. To simulate the situation where a kerosene cigarette lighter is used in accumulated R32, electrodes fixed in the windbreak of the lighter were remotely supplied with electricity to generate sparks of various durations but of similar energies to those of actual sparks generated by rubbing a flint to ignite the fuel in the lighter. We identified several cases of ignition and formation of an open flame in the windbreak of the lighter, and the flame propagated to the accumulated R32 when it was supplied with sufficient energy from the spark. Gas chromatographic analyses confirmed that the mixture in the windbreak of the kerosene lighter consisted mainly of vaporized fuel and air, with no R32. Therefore, even if the lighter is located in accumulated R32, an open flame can be generated in the windbreak of the kerosene cigarette lighter through ignition by the spark energy generated by friction between the flint and the flint wheel. Our results confirmed that there is a real possibility of ignition and flame propagation when a kerosene cigarette lighter is used in accumulated R32 under the leak rate conditions of the present experiment.     

Minimum ignition energy theoretical model for flammable gas based on flame propagation layer by layer

To achieve the rapid prediction of minimum ignition energy (MIE) for premixed gases with wide-span equivalence ratios, a theoretical model is developed based on the proposed idea of flame propagation layer by layer. The validity and high accuracy of this model in predicting MIE have been corroborated against experimental data (from literature) and traditional models. In comparison, this model is mainly applicable to uniform premixed flammable mixtures, and the ignition source needs to be regarded as a punctiform energy source. Nevertheless, this model can exhibit higher accuracy (up to 90%) than traditional models when applied to premixed gases with wide-span equivalence ratios, such as C₃H₈-air mixtures with 0.7–1.5 equivalence ratios, CH₄-air mixtures with 0.7–1.25 equivalence ratios, H₂-air mixtures with 0.6–3.15 equivalence ratios et al. Further, the model parameters have been pre-determined using a 20 L spherical closed explosion setup with a high-speed camera, and then the MIE of common flammable gases (CH₄, C₂H₆, C₃H₈, C₄H₁₀, C₂H₄, C₃H₆, C₂H₂, C₃H₄, C₂H₆O, CO and H₂) under stoichiometric or wide-span equivalence ratios has been calculated. Eventually, the influences of model parameters on MIE have been discussed. Results show that MIE is the sum of the energy required for flame propagation during ignition. The increase in exothermic and heat transfer efficiency for fuel molecules can reduce MIE, whereas prolonging the flame induction period can increase MIE.     

Prevention of gasoline vapor explosions in portable fuel containers

Portable Fuel Containers (PFCs) made for consumer use can, under unusual circumstances, develop a flammable atmosphere in the container headspace. In order to prevent an inadvertent ignition from causing flame propagation into this headspace and a subsequent explosion or flame jetting, PFC manufacturers are developing prototype Flame Mitigation Devices (FMDs) for installation in the PFC. A test method is described in this paper to determine if the installed FMD will indeed prevent flame entry into the PFC in a high-challenge flame propagation scenario. The method entails the use of a butane-air mixture ignited in a 5 cm diameter, 12 cm long tube attached to either the container neck or a spout on the container neck. Two concept FMD designs have successfully prevented repeated attempts at flame propagation into the PFC and have also produced encouraging results in tests for fuel flow restriction, duel dispensing nozzle friction, and prolonged fuel exposure. Versions of these tests are currently being promulgated in a draft ASTM standard on PFC FMDs.     

Flame propagation in lycopodium/air mixtures below atmospheric pressure

Industrial processes are often operated at conditions deviating from atmospheric conditions. Safety relevant parameters normally used for hazard evaluation and classification of combustible dusts are only valid within a very narrow range of pressure, temperature and gas composition. The development of dust explosions and flame propagation under reduced pressure conditions is poorly investigated. Standard laboratory equipment like the 20 l Siwek chamber does not allow investigations at very low pressures. Therefore an experimental device was developed for the investigations on flame propagation and ignition under reduced pressure conditions. Flame propagation was analysed by a video analysis system the actual flame speed was measured by optical sensors. Experiments were carried out with lycopodium at dust concentrations of 100 g/m³, 200 g/m³ and 300 g/m³. It was found that both flame shapes and flame speeds were quite different from those obtained at atmospheric pressure. Effects like buoyancy of hot gases during ignition and flame propagation are less strong than at atmospheric conditions. For the investigated dust concentrations the flame reaches speeds that are nearly an order of a magnitude higher than at ambient conditions.     

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.     

新型气体灭火剂对飞机用橡胶材料的腐蚀性能研究

为研究氢氟烯烃(HFOs)与氢氟氯烯烃(HCFOs)灭火剂对于飞机用橡胶密封材料的腐蚀性,通过实验研究6种新型气体灭火剂(R1234yf,R1234ze,R1234ze-E,R1233xf,R1233zd,R1336mzz-E),对目前飞机用4种橡胶O型圈(硅橡胶VMQ,氟橡胶FKM,氟硅橡胶FVMQ和丁腈橡胶NBR)...     

泄爆口参数对氢气火焰传播过程影响的数值模拟*

为了减少管内气体爆炸造成的损失与破坏,基于大涡模拟LES模型和Zimont燃烧模型,研究泄爆尺寸(直径为40,60,80 mm)和泄爆位置(侧方距点火端1,3,5 m)等泄爆条件对受限空间中氢气燃爆特性的影响。研究结果表明:大孔径泄爆口更好的排放效果造成火焰锋面在通过泄爆口时发生严重畸变,而泄爆口与点火端距离的增加则会削弱火焰锋面畸变的程度,且不同尺寸泄爆口产生的泄压效果差异较大。因此,应考虑将合适尺寸的泄爆口设置于靠近易燃点处。通过探索不同泄爆孔径与泄爆口位置对氢气火焰传播的影响规律,可为实际应用中的安全泄爆起到指导性作用。     

Study of the influence of melamine polyphosphate and aluminum hydroxide on the flame propagation and explosion overpressure of aluminum magnesium alloy dust

When aluminum magnesium alloy dust floats in the air, a certain ignition energy can easily cause an accidental explosion. To prevent and control the occurrence of accidental explosions and reduce the severity of accidents, it is necessary to carry out research on the explosion suppression of aluminum magnesium alloy dust. This paper uses a vertical glass tube experimental device and a 20 L spherical explosive experimental device to carry out experimental studies on the suppression of the flame propagation and explosion overpressure of aluminum magnesium alloy dust with melamine polyphosphate (MPP) and Al(OH)₃. With increasing MPP and Al(OH)₃ concentrations, the flame brightness darkened, the flame velocity and propagation distance gradually decreased, and P_max and (dp/dt)_max decreased significantly. When the amount of MPP added reached 60%, the flame propagation distance decreased to 188 mm, which is a decrease of 68%, and the explosion overpressure decreased to 0.014 MPa, effectively suppressing the explosion of aluminum magnesium alloy dust. The experimental results showed that MPP was more effective than Al(OH)₃ in inhibiting the flame propagation and explosion overpressure of the aluminum magnesium alloy dust. Finally, the inhibitory mechanisms of the MPP and Al(OH)₃ were further investigated. The MPP and Al(OH)₃ endothermic decomposition produced an inert gas, diluted the oxygen concentration and trapped active radicals to terminate the combustion chain reaction.     

Gas explosions caused by gasification of condensed phase combustibles

For reasonable explanation about recent accidental gas explosions caused by condensed phase combustibles occurred in Japan, the processes of such gas explosions have been investigated. When the combustible is of condensed phase at its initial state, gasification is necessary to form a flammable mixture causing a gas explosion. The process of gasification characterizes such a gas explosion. When the combustible is RDF (refuse derived fuel), the temperature was inferred to spontaneously increase. Also, the flammable gas should be generated within a confined high temperature region in the pile and come through a low temperature layer without combustion. The growth of a flammable layer after gasoline is spread over floor is analytically evaluated. The flame propagation through the flammable layer established over the floor enhances the pressure enough to break the structure of the office. Long-term heating is inferred to cause ignition of dried garbage, and the mechanism of flammable gas generation would be similar to that in the case of the RDF explosion. For prevention of losses at accidental explosions caused by gasification of condensed phase combustibles, understanding of the phenomena is the most important.     

Flame propagation behavior of aluminum nanopowder in bulk layer

The flame propagation parameters of aluminum nanopowder in the bulk layer were investigated. The aluminum nanopowder produced by the method of the electrical explosion of wires used in this study. The aluminum bulk layer was ignited by open flame, heated body, or electric spark. The flame propagation behavior is described as a two-stage process: 1) flame propagation over the surface layer and deep into the sample; 2) the thermal explosion mode. It was found that the type of ignition source influences the parameters of the first stage of the combustion. The minimum ignition energy for the aluminum nanopowder bulk layer was measured. The effect of the bulk layer inclination angle on flame propagation parameters was determined. The obtained results can be useful in assessing the fire hazard and organizing safe processes of industrial production during the use, storage, handling, and transportation of metal nanopowders.     

Experimental investigation of limiting oxygen concentration of hybrid mixtures

An investigation into the limiting oxygen concentration (LOC) of fifteen combustible dusts and methane, ethanol and isopropanol hybrid mixtures in the standard 20 L explosion chamber was performed. Three ignition energies (10 J, 2 kJ and 10 kJ) were used. The results show that a 10 J electrical spark ignition leads to significantly higher limiting oxygen concentration values than either 2 kJ or 10 kJ pyrotechnic igniters. This could be due to the “overdriving” effect of the chemical igniters, which produce a hot flame that virtually covers the entire explosion chamber during combustion. With respect to hybrid mixture investigation, the 20 L sphere was modified to allow the input of methane gas and flammable solvents. The limiting oxygen concentrations of the hybrid mixtures were found to be considerably lower than those of dust air mixtures when the relatively weaker spark igniter was used. There was no significant change in limiting oxygen concentration when the higher energy chemical igniters were used.