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- Explosionsschutz (8)
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- Tetrafluoroethylene (6)
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Organisationseinheit der BAM
The classification of flammable gas mixtures is based on either testing or calculation methods proposed by the revised international standard ISO 10156. This standard is used for classification of physical hazards in Chapters 2.2 and 2.4 of the UN Globally Harmonized System of Classification and Labelling of Chemicals (GHS) and in the UN Recommendations on Transport of Dangerous Goods (TDG). The test methods of flammability and oxidizing potential in this standard were developed by BAM. Earlier versions of this standard are not based on triangular diagrams and on the reference combustible substance 'ethane'. The old material characteristics, especially in case of oxidizing potential, are based mostly on practical experience without any quantifiable test results. First time it is possible to compare experimental results from the CHEMSAFE database with the newly developed calculation method. In this paper the basic principles of the calculation methods are presented and the methods are validated by examples. A comparison of experimental flammability data with classification results gained by the calculation methods of ISO 10156 is demonstrated.
In Gasphasen aus Ethylenoxid (EO) und Propylenoxid (PO), die bei technischen Alkoxylierungsreaktionen vorkommen, können auch ohne den Zutritt von Luft Zerfallsreaktionen stattfinden, die explosionsartig mit einer vielfachen Temperatur- und Drucksteigerung verlaufen. Zur Abschätzung der Auswirkungen solcher Explosionen wurden die Explosionsdrücke und die zeitlichen Druckanstiege von reinem EO und EO/PO-Gemischen bei Temperaturen von 100°C bis 200°C und Drücken von 1 - 10 bar in einem 3-dm³-Behälter und punktuell in einem 100-dm³-Behälter experimentell bestimmt.
The hazardous potential of accidental heavy gas releases, especially those involving flammable and toxic gases, is widely known. In order to predict the area in which these gases are in hazardous concentrations, an estimation of the dispersion of these gases must be carried out. While the hazardous area for flammable heavy gases is determined by the lower flammability limit (ca. >1 vol%), the release of toxic heavy gases can result in a much larger hazardous area. Toxic gases, even in very low concentrations (ca. <3,000 ppm), have the potential to be highly damaging. State-of-the-art dispersion models, such as the VDI Guideline 3783, can be used to estimate the dispersion of heavy gases. However, VDI 3783 gives no method for the prediction of the height and width of a heavy gas cloud, which are both required for quantitative risk analysis as well as for a possible coupling of a Lagrangian particle model with the VDI 3783 heavy gas dispersion model. Therefore, further calculation methods were used to describe these dimensions and were evaluated against experimental studies of the length, width, and height of the heavy and neutral gas field. In addition to that the influence of the source height on the heavy gas dispersion was also examined
The paper provides a summary of safety characteristics of hydrogen and hydrogen fuel gases. The inves-tigations focus on water electrolysis, the feeding of hydrogen into the natural gas grid and the use ofhydrogen for the fermentation process in biogas plants. The safety characteristics of hydrogen such as avery low minimum ignition energy, very large explosion range and high flame velocity with the resultingrapid pressure increase of hydrogen explosions are of particular importance for explosion protection andthey differ strongly from those of natural gas. Explosion ranges of hydrogen-methane-carbon dioxidemixtures have been measured for the use of hydrogen in biomethane production. The paper also showsand discusses explosion ranges of hydrogen and hydrogen-natural gas mixtures. Pressure and tempera-ture dependencies of the explosion limits of mixtures were investigated. Furthermore, pressure rise rates(KGvalues) were measured with regard to constructive explosion protection. The maximum experimen-tal safe gaps were determined for the classification of the mixtures and assignment to explosion groupsaccording to the European ATEX directives. It was found that admixture of 10% hydrogen to natural gashas only a minor influence on the safety characteristics of gas explosions.
Validation of the new ignition source 'exploding wire' for dust explosion testing in the 20-L-sphere
(2014)
The safety characteristics Maximum Explosion Pressure pniB, Maximum Explosion Pressure Rise (dp/dt)™* and Lower Explosion Limit LEL are determined in closed vessels such as the 20-L-sphere according to international Standards. Dust ignition is carried out using pyrotechnical igniters which are defined in the Standards. Due to various disadvantages of pyrotechnical igniters the need for alternative ignition sources arises again and again. Studies at the Federal Institute for Material Research and Testing (BAM) with ignition units which were able to generate ignition energies up to 2000 J showed that the so-called “exploding wire” or “fuse wire“ is suitable as an alternative ignition source. The paper presents further test results for the Validation of the exploding wire for the determination of Pm» and (dp/dt)mx in the 20-L-sphere. The tests were performed with a new ignition unit and improved electrodes which allowed ignition energies up to 10000 J. The paper also analyses propagation of flame and electrical arc on basis of high speed camera recordings. Turbulence measurements with a LDA System in the 20-L-sphere allowed investigation whether the activation of the ignition sources has an influence on the turbulence field generated during dust dispersion and whether the influence differs depending on the ignition source.
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.
One of the fundamental principles of the UN-GHS (Globally Harmonized System of Classification and Labelling of Chemicals) is that all hazards of a chemical should be assigned and communicated. There is no general prioritization of hazards in the sense that certain hazard classes are not applicable if another one has been assigned. In contrast to health and environmental hazards, there are physical or chemical factors which preclude certain combinations of physical hazard classes. So far, there is no common understanding as to which combinations are relevant and which not. For example, should a pyrophoric liquid be classified as flammable liquid in addition, or is this redundant and unnecessary? In the course of the implementation of the GHS by countries or sectors and the actual application by industry all over the world, such questions become more and more important.
This publication systematically discusses all combinations of the UN-GHS physical hazard classes and assesses them with regard to the relevance of possible simultaneous assignment to a chemical. For many of the combinations an unambiguous decision based on theGHS alone is not possible, thus confirming that the question which physical hazard classes might be assigned simultaneously to a chemical is not trivial. As one more milestone on the path to a globally harmonized system for the classification of hazardous chemicals, this should be discussed and ultimately solved on a global basis. It is the hope that this publication might serve as an impetus for such discussions.
For evaluation of explosion scenarios in closed systems involving the mildly flammable refrigerants R1234yf, R1234ze and R32 dependent on the ignition energy, ignitions were carried out in a closed autoclave. A newly developed ignition system was used, which allows generating electric arcs with defined energies in a range between 3 J and 1000 J. The lower explosion limit of R32 decreases with increasing ignition energy. R32-explosions can be more severe than explosions involving highly flammable substances.
However, in case of R1234yf and R1234ze, the ignition energy had to be increased to more than 100 J and more than 500 J to detect explosions in the closed system at all, although flame Propagation phenomena can already be observed if these substances are ignited with much weaker ignition sources in open glass tubes. The explosions were very mild with these substances.
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expertevaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.
The flammable hydrogen-blended methane–air and natural gas–air mixtures raise specific safety and environmental issues in the industry and transportation; therefore, their explosion characteristics such as the explosion limits, explosion pressures, and rates of pressure rise have significant importance from a safety point of view. At the same time, the laminar burning velocities are the most useful parameters for practical applications and in basic studies for the validation of reaction mechanisms and modeling turbulent combustion. In the present study, an experimental and numerical study of the effect of hydrogen addition on the laminar burning velocity (LBV) of methane–air and natural gas–air mixtures was conducted, using mixtures with equivalence ratios within 0.90 and 1.30 and various hydrogen fractions rH within 0.0 and 0.5. The experiments were performed in a 14 L spherical vessel with central ignition at ambient initial conditions. The LBVs were calculated from p(t) data, determined in accordance with EN 15967, by using only the early stage of flame propagation. The results show that hydrogen addition determines an increase in LBV for all examined binary flammable mixtures. The LBV variation versus the fraction of added hydrogen, rH, follows a linear trend only at moderate hydrogen fractions. The further increase in rH results in a stronger variation in LBV, as shown by both experimental and computed LBVs. Hydrogen addition significantly changes the thermal diffusivity of flammable CH4–air or NG–air mixtures, the rate of heat release, and the concentration of active radical species in the flame front and contribute, thus, to LBV variation.