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Eingeladener Vortrag
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The Ignition Temperature (IT) of stoichiometric tetrafluoroethylene–air mixtures on hot walls was determined in a 3-dm³-reactor. Tests at elevated pressure conditions were performed, namely at 5, 15 and 25 bar(a), showing a decrease of the IT with the initial pressure. Furthermore, the measured ignition temperatures of stoichiometric tetrafluoroethylene–air mixtures were lower than the ignition temperatures required for the decomposition pure tetrafluoroethylene (Minimum Ignition Temperature of Decomposition, MITD) reported in previous works.
Equations from the Semenov thermal explosion theory on spontaneous ignition were used to identify approximate combustion kinetics of tetrafluoroethylene from the experimental results. The determined kinetics was used for the prediction of the IT of stoichiometric tetrafluoroethylene-air by simplified calculation methods. A very good agreement with the experimental results was observed.
This work investigates the ignition of tetrafluoroethylene induced by the adiabatic compression that can arise by activating a high speed valve separating two portions of a pipeline with a high pressure difference. In the tests performed the high pressure zone contained tetrafluoroethylene at pressures between 15 and 30 bar. For the low pressure zone, experiments with nitrogen, air and tetrafluoroethylene were carried out. The pressure range in the low pressure zone was comprised between 0.05 and 1 bar. The pipe diameters analyzed were 15 and 20 mm. For the analyzed geometries, special conditions were required in order to reach reproducible ignitions, namely air at temperatures of at least 105 °C had to be present in the compression pipe. Furthermore, a minimum length of the compression pipe had to be used. The current work describes the experimental setup employed for the tests and discusses the achieved results. Numerical simulations were performed in order to clarify unexpected findings.
Die adiabate Kompression stellt insbesondere für zerfallsfähige Gase eine potentielle Zündquelle sowohl bei Herstellungsprozessen als auch beim Umgang in weiter-verarbeitenden Betrieben oder beim Endnutzer dar. Unter bestimmten Bedingungen kann hier eine explosionsartige Zerfallsreaktion auch in Abwesenheit eines Oxidators initiiert werden. Zur systematischen Untersuchung des Zündverhaltens von Zerfallsreaktionen wurde eine Rohrapparatur mit einem schnell öffnenden Kugelhahn aufgebaut, um praxisnahe Vorgänge darstellen zu können. Am Beispiel Tetrafluorethen (TFE) wurden umfangreiche Untersuchungen mit unterschiedlichen Rohrdurchmessern und –längen durchgeführt. Neben der Kompression von homogenen Gasphasen wurden außerdem Kompressionsvorgänge von heterogenen Gasen durchgeführt. Dabei war das Gas im Niederdruckteil unterschiedlich zum Gas im Hochdruckteil. Für den Hochdruckteil wurde Stickstoff, Acetylen und TFE verwendet. Im Niederdruckteil kamen TFE, Stickstoff und Luft zum Einsatz. Zudem wurden das Kompressionsverhältnis sowie die Absolutdrücke im Hochdruck- und Kompressionsteil variiert. Für TFE wurde ein Druckbereich bis 30 bar absolut untersucht. Versuche mit Acetylen wurden zur apparativen Validierung durchgeführt. Es zeigte sich, dass in der verwendeten Apparatur reproduzierbare Zündvorgänge nur im Bereich sehr enger Anfangsparameter möglich sind. Die Kompression von Luft durch ein zerfallsfähiges Gas stellt dabei den sicherheitstechnisch kritischsten Fall dar.
Adiabatic compression of gases can work as an ignition source and is still one of the main causes of accidents in chemical plants processing tetrafluoroethylene (Reza and Christiansen, 2007). The ignition of tetrafluoroethylene induced by adiabatic compression has been studied experimentally with a setup which allowed for the rapid opening of a high speed valve connecting two portions of a pipeline at different initial pressures. Due to the fast opening time and to the high pressure difference, a shock wave in the pipeline was generated. The propagation of the shock wave and its reflection at the end of the pipeline caused pressure and temperature increase. This led to some ignitions in the experiments performed. Nonetheless, in some test an ignition was not achieved, even if this was expected according to the theoretical temperatures predicted by the Rankine-Hugoniot equations. In order to understand the discrepancy between the experimental results and the theoretical predictions, shock wave simulations have been carried out with COMSOL Multiphysics. The 'High Mach Flow' interface was used, since it solves the heat and impulse equations for fast flows. Figure 1 and Figure 2 show, respectively, the velocity and temperature distribution over time for a simulation in a 0.2 m pipeline of 20 mm in diameter with the following settings:
- high pressure section: nitrogen initially at 20 bar;
- low pressure section: nitrogen initially at 1 bar;
- initial temperature of the system: 20 °C;
- adiabatic walls with slip condition for the flow;
- laminar flow.
As from Figure 1 and Figure 2 the shock wave generation and propagation has been properly computed and the physical properties of the shock wave reflected the prediction of the Rankine-Hugoniot equation. Nonetheless, divergence problem occurred when trying to add turbulence to the system and strange temperature and profiles after the shock wave reflection were achieved if the no slip condition at the walls was chosen. Despite these limitations, it was possible to perform a parametric study and to analyze the effect of the pipe diameter and length on the shock wave evolution. Here simulations with constant wall temperature were carried out, in order to account for the heat losses to the pipe surroundings. Figure 3 shows that the temperature of the reflected wave is maintained for a longer time, if the pipe diameter is larger, due to minor heat losses. On the other hand, Figure 4 shows that higher average temperatures are achieved and maintained for a longer time if the pipe length increases. These results suggest that in the experiments performed by Meyer (2009) the pipe geometry was probably not optimal for the achievement/conservation of high temperatures and might explain the difficulty in inducing ignitions by adiabatic compression.