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.     

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.     

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.     

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。     

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.     

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.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

Experimental and numerical study of the fuel effect on flame propagation in long open tubes

Previous works (Daubech et al., 2019) were dedicated to gaseous flame acceleration along long pipes with a set of cases studied both experimentally and numerically. In these cases, the flammable mixture was initially quiescent and homogenously distributed. The impact of the tube diameter and material were studied trough both approaches for rather slow flames, the fuel being methane. While main features of the real flame were recovered by the chosen CFD method, some limits remained.A new experimental dataset is detailed and analyzed with a quicker flame, the fuel being hydrogen and the same experimental set-up as the one used for measuring slow flames. Thus, the fuel effect on the flame dynamics can be directly highlighted.A simple CFD approach is tested for recovering two distinct flame behaviors: a deflagration flame and another undergoing deflagration-to-detonation transition. Furthermore, the modelling results are used to propose elements of interpretation for flame acceleration.     

Ignition hazard evaluation on A2L refrigerants in situations of service and maintenance

To restrict the progress of the global warming, A2L refrigerants such as 2,3,3,3-tetrafluoroprop-1-ene (R1234yf), (Z/E)-1,3,3,3-tetrafluoroprop-1-ene (R1234ze), and difluoromethane (R32) have been expected of alternatives to the standard refrigerants currently in use. The ignition hazard of A2L refrigerants under plausible accident situations in service and maintenance was examined experimentally for two cases: leakage of an A2L refrigerant from a pinhole in a pipe or hose (Scenario 1), and leakage of an A2L refrigerant into an item of equipment used for service and maintenance, such as a collection device (Scenario 2). In Scenario 1, the location of the flammable zone and the possibility of a jet flame being formed instantaneously on contact with an ignition source were examined. Even when R1234yf leaked from a 4 mmϕ pinhole (corresponding to breakage of a pipe), the flammable zone extended only about 10 cm from the pinhole in the downstream region. In an ignition test with a continuous spark as the ignition source, a pale emission appeared only near the spark, and the flame did not propagate to the rest of the refrigerant jet. In Scenario 2, the accumulation and ignition behaviors of A2L refrigerants in a model collection device were examined experimentally. Ignition and flame propagation occurred in a test on a model collection device lacking slits, whereas when slits wider than 20 mm were present, ignition and flame propagation did not occur. Even if R1234yf leaked into the model collection device, provided that slits of an effective width were present, the R1234yf could diffuse through slits and barely accumulated, and no ignition or flame propagation occurred.     

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.     

Study on the preparation of novel FR-245/MCM-41 suppressant and its inhibition mechanism on oil shale deflagration flame

Oil shale development is of great significance because oil and gas resources are scarce. Research on the prevention of oil shale dust explosion is particularly important for guaranteeing the safe development and utilization of oil shale resources. In this work, the flame morphology and velocity of oil shale dust with and without MCM-41 or FR-245 were compared. Furthermore, the novel green FR-245/MCM-41 inhibitor was prepared by jet mill method and used in oil shale dust explosion for the first time. The best ratio of FR-245/MCM-41 for flame inhibition was obtained, which was 9: 1. The pyrolysis oxidation behavior of oil shale before and after adding FR-245/MCM-41 was analyzed and compared by FWO and KAS methods, respectively. The results showed that the activation energy calculated by FWO and KAS methods greatly increased after adding FR-245/MCM-41, which increased by 95.36% and 115.15% than that before adding inhibitor, respectively. Significantly, the activation energy is particularly high for two methods when α between 0.2 and 0.6, due to that MCM-41 and FR-245 coexisted to limit the oxidation of oil shale. For α between 0.7 and 0.9, the activation energy is still high because of the existence of MCM-41. Combining the oil dust flame propagation behavior with the characterization results before and after explosion, the physical-chemical synergy mechanism of oil dust flame propagation inhibition was revealed.     

化学品事故应急响应中危害距离的确定

介绍了不同国家、机构确定的毒性物质、易燃易爆物质紧急暴露限值和化学品事故中危害距离的确定方法，并以液氯钢瓶泄漏事故说明毒性危害距离的确定，以天然气管线泄漏火灾、爆炸事故说明火灾爆炸事故危害距离的确定。     

井喷失控点火时间与方位探讨

利用计算流体力学方法(CFD)对井喷失控后天然气扩散过程进行研究,在有限元基础上建立模型,采用κ-ε紊流模型求解得出井喷失控后可燃性蒸气云随时间、风速变化的影响情况,求出稳态以后易爆区域的蒸气云形状。取5.0%和15%作为甲烷的爆炸上、下限,在不同区域进行点火求解爆燃结果,通过比较给出推荐的点火时间和点火方位。该研究成果可对井喷失控蒸气云爆燃危害性进行预测,有助于指导井喷失控进行点火放喷工作,避免爆燃事故的发生。     

Determination of the performance limits of flame arresters at increased oxygen concentrations

This investigation shows how an increased oxygen concentration influences the performance limits of crimped ribbon deflagration flame arresters at elevated pressures. An evaluation of the maximum experimental safe gap (MESG) as reliable criterion for describing the performance limits under non-atmospheric conditions is given. Measurements of MESGs and flame arrester performance tests were performed. Various fuel/oxygen/air mixtures containing ethylene and propane were used as testing gases. Former studies on the pressure dependence and the influence of oxygen on the MESG were initially confirmed. Furthermore, performance tests using a commercial deflagration flame arrester revealed that such a flame arrester may prevent flame transmission also at non-atmospheric conditions within a limited range. For various oxygen concentrations the performance limits were reached at the same MESG. Hence, it can be assumed that a flame arrester possesses a device- and fuel-specific maximum experimental safe gap for a specific gas mixture in different concentrations and at different pressures. This performance-related maximum safe gap can be used as a parameter for estimating and describing the performance limits of a flame arrester. It offers an attempt to simplify the testing and qualification of deflagration flame arresters for non-atmospheric conditions.     

Venting of Low Pressure Hydrogen Gas: A Critique of the Literature

The use of hydrogen is increasing in industrial processes, and its use is likely to increase further with its potential use as an energy carrier. The venting of hydrogen is inevitable at some time for almost all uses, and its propensity to ignite makes it essential that safe venting regimes are understood. The options for disposal by dilution to below the lower flammable limit, inerting, dispersion of flammable concentrations and flaring are discussed, along with the potential for ignition of releases within the flammable range and the subsequent need for flame extinguishing. The available literature on the protection of vents from external ignition is critically examined, to determine the appropriate parameters to allow selection of a disposal method. A decision-tree is presented to allow a rational appraisal of the most appropriate disposal method to be selected and precautions to be applied for adequate protection of the vent.     

抑制煤矿瓦斯爆炸传播的新技术设想

基于石油阻火装置对可燃气体爆炸传播的火焰具有淬熄作用,对压力波具有抑制作用,提出将金属丝网、波纹板型等几种结构用于抑制煤矿瓦斯爆炸传播的新思路,填补了阻火器在煤矿中应用的空白,为煤矿阻隔爆技术开拓出新的领域.     

多元可燃混合溶液的闪点预测

为了预测多元可燃混合液的闪点,建立了一个预测模型,通过二元和三元可燃混合液闪点实测值的试验对比,证实此模型的误差在可接受的范围内。此模型可以在预知可燃混合液组分比例和单组分闪点基础上快速预测混合液的闪点。     

The quenching of propane deflagrations by crimped ribbon flame arrestors

Experimental studies of deflagration flame quenching by crimped ribbon flame arrestors were performed in a circular ducting with propane-air flammable mixture. The corresponding flameproof velocities were determined systemically. The results showed that the channel length, the expansion ratio and the aperture size must be taken into consideration to predict the performance of the crimped ribbon flame arrestors. To explore the relationship between flameproof velocity and arrestor structure, numerical simulations were carried out. The simulated results showed that with the reduction of the hydraulic diameter of the aperture size, the flameproof velocity is increased, which implies the basic angle must be considered when crimped ribbon flame arrestors are used to quench deflagration flame. In addition, the influence of the expansion ratio is of great significance on the efficiency of flame arrestors. The flameproof velocity can be reduced to be a value related to the expansion ratio. Two empirical formulas were derived to exhibit the relation between the flameproof velocity and the characteristics of the flame arrestor, which can be used to predict the performance of crimped ribbon arrestors.     

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.     

池火特性参数计算及其热辐射危害评价

可燃性油品池火的火焰及其产生的热辐射 ,可能导致周围人员伤亡或设备设施损坏。笔者介绍了油品池火的质量燃烧速率、火焰长度、火焰倾角及火焰后拖量等特性参数的计算方法 ,提出了池火热辐射强度的预测模型 ,给出了热辐射伤害 /破坏准则 ,并进行了模拟计算和评价。