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Eingeladener Vortrag
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Druck-Abbau
(2003)
The explosive properties of mixtures of aqueous hydrogen peroxide (H2O2) and different alcohols (ROH) like 2-propanol (2-PropOH), 2-methyl-2-propanol (TBA), 2-methyl-2-butanol (TAA) and 2-methyl-2-pentanol (THA) were investigated. Among others, the potential hazard of such mixtures may be characterized by their ability to react by different mechanisms of an explosion in the condensed phase, e.g. the thermal explosion or the detonation. Accordingly, the mixtures were experimentally investigated either by heating them up under confinement in different autoclaves or by exposing them to a shock wave impact applying the steel tube test. The results are discussed and compared to literature data.
Tests according to the UN Recommendations on the Transport of Dangerous Goods for the determination of explosive properties of organic peroxides have been compared with screening criteria for explosivity based on measurements in a closed mini-autoclave (MCPVT). It will be shown that an additional screening test may be helpful but the information obtained from the UN tests are more important to characterise the specific properties of a substance under different conditions.
In the UN H.4 test a suitable test to determine the SADT for solids in a 50kg packaging or not?
(2003)
Many self-accelerating decomposition temperatures (SADTs) of solid organic peroxides and self-reactive substances have been determined with the UN test method H.4, which is a scaled down test in a small Dewar vessel. For solid organic peroxides and solid self-reactive substances Fierz has questioned this procedure in a recent paper. Fierz concluded that the Dewar test results should not be extrapolated to beyond 8 l packages, owing to the thermal insulation value of solids. On the other hand, long term experience with the test, with a great variety of solid organic peroxides and self-reactive substances show about equal critical temperatures in the small Dewar vessel and on 50 kg scale. In the present work, we first checked, by numerical simulations, the Dewar scale versus the larger scale, in a way comparable with Fierz method: both scales are simulated by spheres, consisting of a number of annular layers, for the large scale the usual external heat loss term is used but for the small scale the outside heat transfer is strongly limited. The outcome of these simulations, covering a variety of physical parameters, supports the concerns expressed by Fierz. After this, we performed accurate cooling and heating experiments with solid organic peroxide in the usual Dewar vessel, provided with a large set of thermocouples. The results of these experiments showed that the simulation model for the Dewar vessel has to be changed from a spherical analogue to a short cylinder of solid material with heat exchange mainly via its top (Utop 3.5 W/(m2 K), overall heat transfer coefficient) and some heat exchange (Uside 0.29 W/(m2 K)) through its cylindrical and bottom part. With this modified cylinder model (being neither an infinitely long cylinder nor a slab) of the Dewar vessel, we found that the UN method H.4 enables an accurate prediction of the SADT, with small deviations of 0 ± 2.5 °C. Further, by performing a truly three-dimensional (3D) finite element calculation in FEMLAB, the new heat characteristics of the Dewar vessel as well as a 50 kg package of dilauroyl peroxide, a solid organic peroxide, were checked. The outcome was compared with the critical ambient temperatures known for various package sizes, which agreed well.
Staubexplosionen können in nahezu allen Branchen auftreten, in denen brennbare Schüttgüter und Stäube gehandhabt werden oder entstehen können, vor allem dort, wo Stäube in aufgewirbelter Form vorkommen. Abgelagerte Stäube können bei starker Erwärmung zur Entzündung gelangen. Die Beurteilung daraus entstehender Gefahren und das Auslegen von vorbeugenden und konstruktiven Schutzmaßnahmen erfolgt über sog. sicherheitstechnische Kenngrößen (STK). Im Rahmen eines vom Bundesland Sachsen geförderten Projekts sind von der Bundesanstalt für Materialforschung und -prüfung (BAM) STK brennbarer Stäube zu Staubgruppen zusammengefasst und in den Gemeinsamen Stoffdatenpool Bund/Länder (GSBL) integriert worden. Grundlage für die Staubgruppen waren zahlreiche Datensätze, die in der Datenbank GESTIS-STAUB-EX des Instituts für Arbeitsschutz der Deutschen Gesetzlichen Unfallversicherung (IFA) veröffentlich sind. Angegeben werden allerdings nicht mehr die dort enthaltenen Kenngrößen einzelner Stäube, sondern Bandbreiten, innerhalb derer sich die STK der in den Staubgruppen zusammengefassten Stäube bewegen können. Je nach Datenlage wurden die sicherheitsrelevanten Grenzen dieser Bandbreiten mit einem Ranking versehen.