Ingenieurwissenschaften und zugeordnete Tätigkeiten
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Organisationseinheit der BAM
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 (LELN2O) to the lower explosion limit in air (LELair) is 0.52 and the ratio of the maximum oxygen content in air (MOCair) to the limiting oxidizer fraction in nitrous oxide (LOFN2O) 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.
The explosion regions of 1-propanol, 2-propanol, acetone and 1-butanol in air were measured in the presence of CO2, He, N2 and Ar in accordance with EN1839 method T at high temperatures and at atmospheric pressure. The experimental results show that 1-propanol, 2-propanol and acetone have very similar lower explosion limits (LELs). 1-Butanol shows a slightly wider explosion area near the LEL line. In addition, the explosion regions of all combustible/inert gas/air mixtures were calculated with the method of constant adiabatic flame temperature profiles (CAFTP), using the flame temperature profile along the explosion region boundary curve of each combustible/N2/air mixture as a reference to determine the explosion regions of combustible/inert gas/air mixtures with inert gases other than N2 at different initial temperatures. To calculate the explosion regions for systems containing He, the calculation method was modified to include the very different physical transport properties of He. Moreover, the procedure for calculating the apexes in the ternary explosion diagrams was modified. The calculation results show good agreement with the experimental results.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given here of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and its new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This article summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under non-atmospheric conditions are given.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given in this review of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and ist new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 flammable liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This review summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under nonatmospheric conditions are given.
The Globally Harmonized System of Classification and Labelling of Chemicals (UN-GHS) is being implemented in more and more countries all over the world; the EU has done so with the CLP-Regulation (EU-CLP). Compared to the undeniably important questions on health and environmental hazards, the classification of physical hazards of chemicals often has not been in the focus, although their implementation can be challenging and there are traps and pitfalls to be avoided. The following overview of the classification systematics for physical hazards aims at a principle understanding without detailing all criteria or test methods. Similarities and differences between the classification systems of the UN-GHS and EU-CLP, the transport of dangerous goods and the former EU system are reviewed with regard to the physical hazard classes. Available physical hazard classifications for the transport of dangerous goods and according to the former EU system can be used as available information when classifying according to the GHS. However, the interfaces of these classification systems and their limitations have to be understood well when concluding on GHS/CLP classifications. This applies not only to industry when applying CLP but especially to legislators when adapting legislation that in one way or another refers to the classification of chemicals.
The test methods UN Test L.2 / EN ISO 9038:2013 DIN EN 15188:2007 are applied to characterize the sustained combustibility of liquids i.e. the behaviour of a material under specified test conditions, whereby its vapour can be ignited by an ignition source and sufficient flammable vapour is produced to continue burning for at least 15 s after the source of ignition has been removed.
The aims of this interlaboratory test (IT) are the verification and/or the improvement (if necessary) of the verification data (reference material) in Annex B of EN ISO 9038:2013, the assessment of influencing (disturbing) factors (laboratory specific factors, which possibly may have an influence on the test result) and the assessment of the performance of the participating laboratories.
It could be demonstrated that the reference materials n-Dodecane, n-Decane and n-Undecane as mentioned in the standard are suitable and the verification shall continue to be valid.
Sustained combustibility tests are influenced by several factors like the presence of a draught shield, the experience of the laboratory assistant, verification of the apparatus, calibration of the metering device.
Based on the interlaboratory test, the gained experience and the actual results, well-founded measures / actions can be recommended to improve execution of the method.
The IT was organized by PTB, BAM and QuoData GmbH in the framework of the co-operation project CEQAT-DGHS Centre for Quality Assurance for Testing of Dangerous Goods and Hazardous Substances.
Explosion regions of propane, isopropanol, acetone, and methyl acetate/inert gas/air mixtures
(2016)
The explosion regions for propane, isopropanol, acetone, and methyl acetate with air in the presence of nitrogen, argon, helium, and carbon dioxide were determined experimentally according to EN 14756/EN1839, method T. Except for propane, all the measurements were executed at 323 K and 1 bar. Propane experiments were carried out at 293 K and 1 bar. The results show that for the same type of inert gas, propane, isopropanol, and acetone have great closeness concerning the concentration of the inert gas at the apex of the explosion envelope in a ternary diagram with air as oxidizer. This leads to consistency in the limiting oxygen concentration (LOC) and minimum required amount of inert gas (MAI) values. Concerning methyl acetate, the apex was always reached at higher percentages of inert gases compared with the other fuels. This can be attributed to the presence of two oxygen atoms inside the chemical structure. Calculation of the explosion regions was carried out based on calculated adiabatic flame temperature (CAFT) method. The flame temperatures for the experimentally determined fuel/air/N2 mixtures were calculated. Then, these temperatures were used to predict the explosion limits of similar mixtures with other inert gases than nitrogen. The modeling results show reasonable agreement with the experimental results.
Many industrial processes are run at non-atmospheric conditions (elevated temperatures and pressures, other oxidizers than air). To judge whether and if yes to what extent explosive gas(vapor)/air mixtures will occur or may be generated during malfunction it is necessary to know the safety characteristic data at the respective conditions. Safety characteristic data like Explosion limits, are depending on pressure, temperature and the oxidizer. Most of the determination methods are standardized for ambient conditions.
In order to obtain determination methods for non-atmospheric conditions, particularly for higher initial pressures, reliable ignition criteria were investigated. Ignition tests at the explosion Limits were carried out for mixtures of methane, propane, n-butane, n-hexane, hydrogen, ammonia and acetone in air at initial pressures up to 20 bar. The tests have been evaluated according to different ignition criteria: visual flame propagation, temperature and pressure rising. It could be shown that flame propagation and occasionally self-sustained combustion for several seconds occurred together with remarkable temperature rise, although the pressure rise was below 3%. The results showed that the combination of a pressure rise criterion of 2% and a temperature rise criterion of 100 K seems to be a suitable ignition criterion for the determination of explosion limits and limiting oxidizer concentration at higher initial pressures and elevated temperatures. The tests were carried out within the framework of a R&D project founded by the German Ministry of Economics and Technology.