On the flammability limits of saturated vapours of hydrocarbons

The upper flammability limits of saturated vapours of four hydrocarbons (cyclohexane, benzene, toluene and ethylbenzene) in oxygen—nitrogen and oxygeThe different reactivity of the four hydrocarbons is discussed, taking into account the pressure dependence of the flammability limits, which appeared     

Carbon dioxide dilution effect on flammability limits for hydrocarbons

Theoretical models to predict the upper/lower flammability limits of a mixture composed of hydrocarbon and inert carbon dioxide are proposed in this study. It is found theoretically that there are linear relations between the reciprocal of the upper/lower flammability limits and the reciprocal of the molar fraction of hydrocarbon in the hydrocarbon/inert gas mixture. These theoretical linear relations are examined by existing experimental results reported in the literature, which include the cases of methane, propane, ethylene, and propylene. The coefficients of determination (R(2)) of the regression lines are found to be larger than 0.959 for all aforementioned cases. Thus, the proposed models are highly supported by existing experimental results. A preliminary study also shows the conclusions in present work have the possibility to extend to non-hydrocarbon flammable materials or to inert gas other than carbon dioxide. It is coincident that the theoretical model for the lower flammability limit (LFL) in present work is the same as the empirical model conjectured by Kondo et al.     

三元混合物的爆炸极限实验

参照国标GB/12474-90的有关规定,设计了一套测试可燃气体爆炸极限的实验装置。系统地测量了三元混合物R290+R152a+R134的爆炸极限,积累了爆炸极限数据,绘制了爆炸极限曲线。混合物的临界爆炸比(CFR),随着R290/R152a体积比的增大而增大。     

A study on flammability limits of fuel mixtures

Flammability limit measurements were made for various binary and ternary mixtures prepared from nine different compounds. The compounds treated are methane, propane, ethylene, propylene, methyl ether, methyl formate, 1,1-difluoroethane, ammonia, and carbon monoxide. The observed values of lower flammability limits of mixtures were found to be in good agreement to the calculated values by Le Chatelier's formula. As for the upper limits, however, some are close to the calculated values but some are not. It has been found that the deviations of the observed values of upper flammability limits from the calculated ones are mostly to lower concentrations. Modification of Le Chatelier's formula was made to better fit to the observed values of upper flammability limits. This procedure reduced the average difference between the observed and calculated values of upper flammability limits to one-third of the initial value.     

On the temperature dependence of flammability limits of gases

Flammability limits of several combustible gases were measured at temperatures from 5 to 100 °C in a 12-l spherical flask basically following ASHRAE method. The measurements were done for methane, propane, isobutane, ethylene, propylene, dimethyl ether, methyl formate, 1,1-difluoroethane, ammonia, and carbon monoxide. As the temperature rises, the lower flammability limits are gradually shifted down and the upper limits are shifted up. Both the limits shift almost linearly to temperature within the range examined. The linear temperature dependence of the lower flammability limits is explained well using a limiting flame temperature concept at the lower concentration limit (LFL)--'White's rule'. The geometric mean of the flammability limits has been found to be relatively constant for many compounds over the temperature range studied (5-100 °C). Based on this fact, the temperature dependence of the upper flammability limit (UFL) can be predicted reasonably using the temperature coefficient calculated for the LFL. However, some compounds such as ethylene and dimethyl ether, in particular, have a more complex temperature dependence.     

Experimental study of flammability limits of natural gas-air mixture

Flammability limits data are essential for a quantitative risk assessment of explosion hazard associated with the use of combustible gas. The present work is to obtain the fundamental flammability data for prevention of the hazards in the practical applications. Experiments have been conducted in a constant volume combustion bomb, and the fuel considered here is natural gas (NG). The pressure histories in the combustion bomb are recorded and a criterion of 7% pressure rise has been used to judge a flammable mixture. The effects of ethane on NG-air flammability limits have been investigated. By adding diluent (carbon dioxide, nitrogen or their mixture) into NG-air mixture, the dilution effects on the flammability limits have been explored as well, and the results are plotted as functions of diluent ratio.     

Experimental exploration of discrepancies in F-number correlation of flammability limits

Flammability limits measurement has been made by ASHRAE method for some 20 kinds of combustible gases and vapors. These compounds have been selected mainly because the literature values of flammability limits are not consistent with the F-number calculated ones [J. Hazard. Mater. A 82 (2001) 113]. As a result, it has been found that the newly obtained values of flammable range are classified into three groups. For the first group of compounds, the present values agree well to the literature values. For the second group, the present values do not agree to the literature values but agree with the calculated ones. For the third group ones, the present values neither agree to the literature values nor to the calculated ones. There are 4, 13, and 6 compounds in the respective groups.     

Effect of vessel size and shape on experimental flammability limits of gases

The flammability limits of methane and propane have been measured using cylindrical vessels of various sizes and one spherical vessel. An ac discharge ignition method has been employed. For a cylindrical vessel of small diameter with a large height, the flammability limits are primarily determined by the quenching effect of the wall. For cylindrical vessels of smaller heights, the experimental flammability limits are affected by hot gas accumulation at the vessel ceiling, unburned gas heating, self heating of the incipient flame by the reflection both from walls and ceiling, and the quenching effect of the walls. If the vessel size is large enough so that all these effects become negligible, the experimental values of flammability limits may approach to the values that would be obtained in free space. In order to approach this condition for a cylindrical vessel, it is desirable to use a container at least 30 cm in diameter and 60 cm in height. For comparison purpose, the measurement has also been done using ASHRAE type 12l spherical flask.     

Experimental study of the flammability limits of toluene-air mixtures at elevated pressure and temperature

The flammability limits of toluene–air mixtures are experimentally determined at pressures up to 500 kPa and temperatures up to 250°C in a closed spherical vessel. The results at atmospheric pressure are compared with the results obtained in a glass tube. The flammability limits depend linearly upon temperature. A twilight zone characterized by weak pressure rises is observed for toluene at all pressures, while soot is formed at elevated pressures only. The explosion characteristics of toluene are compared with those of methane. Despite their chemical differences, the explosion characteristics of toluene and methane are similar.     

Extended Le Chatelier's formula for carbon dioxide dilution effect on flammability limits

Carbon dioxide dilution effect on the flammability limits was measured for various flammable gases. The obtained values were analyzed using the extended Le Chatelier's formula developed in a previous study. As a result, it has been found that the flammability limits of methane, propane, propylene, methyl formate, and 1,1-difluoroethane are adequately explained by the extended Le Chatelier's formula using a common set of parameter values. Ethylene, dimethyl ether, and ammonia behave differently from these compounds. The present result is very consistent with what was obtained in the case of nitrogen dilution.     

Evaluation of lower flammability limits of fuel-air-diluent mixtures using calculated adiabatic flame temperatures

The lower flammability limit (LFL) of a fuel is the minimum composition in air over which a flame can propagate. Calculated adiabatic flame temperatures (CAFT) are a powerful tool to estimate the LFL of gas mixtures. Different CAFT values are used for the estimation of LFL. SuperChems is used by industry to perform flammability calculations under different initial conditions which depends on the selection of a threshold temperature. In this work, the CAFT at the LFL is suggested for mixtures of fuel-air and fuel-air-diluents. These CAFT can be used as the threshold values in SuperChems to calculate the LFL. This paper discusses an approach to evaluate the LFL in the presence of diluents such as N2 and CO2 by an algebraic method and by the application of SuperChems using CAFT as the basis of the calculations. The CAFT for different paraffinic and unsaturated hydrocarbons are presented as well as an average value per family of chemicals.     

The influence of different diluents on the flammability limits of ethylene at high temperatures and pressures

For the safe design and operation of many chemical processes, it is necessary to know certain flammability limits at high temperatures and pressures. Despite the great importance of such safety problems, few data are available in the literature, and those available are unreliable. This is due to the experimental difficulties involved.In this paper the different methods proposed for such measurements are critically discussed: the double-filling system appears to be the most suitable for avoiding the slow oxidation reactions before ignition. Flammability data up to 250°C amd 20 atm for ethylene-oxygen mixtures with different diluents (nitrogen, carbon dioxide, methane) are presented.     

The lean flammability limits in air of methane,hydrogen and carbon monoxide at low temperatures

The lean flammability limits in air for methane, hydrogen and carbon monoxide at atmospheric pressure were established under isothermal initial conditions at temperatures extending down to ?130°C. Simple guidelines are then suggested for predicting these limits on the basis of the calculated flame temperature of the limiting mixtures. Estimates were also made of the extent of changes in these limits due to heat transfer over a wide mixture temperature range.     

Prediction of flammability of gases by using F-number analysis

A novel method of predicting flammability limits has been proposed. This method utilizes a new flammability index called F-number. For this purpose, an empirical expression of F-number has been derived to account for the flammability characteristics of various organic substances. The analysis has been done by fitting to the observed values of F-number for a wide variety of organic gases and vapors. As a result, it has been found that F-number is an excellent tool to analyze the flammability characteristics of various substances. It has also been shown that the values of upper and lower flammability limits can be derived from F-number together with the stoichiometric concentration corrected for the effect of selective diffusion.     

瓶装氮气中22组分挥发性卤代烃混合气体标准物质的研制

介绍瓶装1μmol/mol氮气中22组分挥发性卤代烃混合气体标准物质的研制过程。以22种挥发性卤代烃高纯试剂为原料,采用称量法制备并计算定值,评定制备过程引入的不确定度、以及均匀性和稳定性引入的不确定度,并将研制的标准物质送至中国计量科学研究院进行测试比对,采用En值评定比对结果,结果显示En值均1,所有组分比对结果判定均为满意,验证研制标物定值结果的准确性。该气体标准物质获得国家二级气体标准物质证书,编号为GBW(E)062232,其定值的相对扩展不确定度为U=5.0%(k=2),有效期限为12个月。     

Comparison and evaluation of methods for the determination of flammability limits, applied to methane/hydrogen/air mixtures

Different methods, both experimental and numerical, to determine the flammability limits are compared and evaluated, exemplified by a determination of the flammability limits of methane/hydrogen/air mixtures for hydrogen fuel molar fractions of 0, 0.2, 0.4 and 0.6, at atmospheric pressure and ambient temperature. Two different experimental methods are used. The first method uses a glass tube with visual observation of the flame, whereas the second method uses a closed spherical vessel with a pressure rise criterion to determine whether flame propagation has occurred. In addition to these experiments, the flammability limits are determined numerically. Unsteady planar and spherically expanding flames are calculated with a one-dimensional flame code with the inclusion of radiation heat loss in the optically thin limit. Comparison of the experimental results with the results of the planar flame calculations shows large differences, especially for lean mixtures. These differences increase with increasing hydrogen content in the fuel. Better agreement with the experimental results is found for the spherically expanding flame calculations. A limiting burning velocity of 5 cm/s is found to predict the upper flammability limit determined with the tube method very well, whereas the limiting flame temperature approach was found to give poorer agreement. Further analysis indicates that the neglect of flame front instabilities is the probable cause of the large differences between experimental and numerical results at the lower flammability limit.