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- Self-ignition (7)
- Tetrafluoroethylene (6)
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Eingeladener Vortrag
- nein (10)
Die Menge an genutztem, verarbeitetem und gelagertem Holz steigt von Jahr zu Jahr. In der Folge konnte in den letzten fünf Jahren eine deutlich gestiegene Zahl von Bränden in Holzlagern und -halden festgestellt werden. Viele dieser Brände sind durch Selbstentzündung des Materials verursacht worden. Sind die Ursachen der Selbstentzündung bekannt, kann die Brandentstehung durch geeignete Maßnahmen vermieden werden. Die Fachgruppe II.2 „Reaktionsfähige Stoffe und Stoffsysteme“ der Bundesanstalt für Materialforschung und -prüfung hat in diesem Leitfaden das Thema aufgegriffen und die derzeit vorliegenden Erkenntnisse zusammenfassend dargestellt. Ziel des Leitfadens ist es, die Grundlagen der Selbstentzündung von Biomasse am Beispiel von Holz in übersichtlicher Form darzustellen und daraus praktische Hinweise zur Vermeidung der Selbstentzündung von Holzhalden abzuleiten, um so einen Weg für einen sicheren und nachhaltigen Umgang mit diesem Rohstoff zu ebnen. Dem Leitfaden liegen Ergebnisse des Forschungsvorhabens „Brandvermeidung bei der Lagerung von biogenen Brennstoffen“ zugrunde. Das Projekt wurde innerhalb der Fördermaßnahme „klimazwei – Forschung für den Klimaschutz und Schutz vor Klimawirkungen“ des Bundesministeriums für Bildung und Forschung finanziell gefördert (Förderkennzeichen 01LS05079). Für diese Förderung möchten die Autoren sich bedanken.
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.
There is a lack of data on the self-ignition behaviour of tetrafluoroethylene (TFE) in industrial sized
equipment. In order to assess the tendency of TFE for
decomposition in large scale vessels, , a facility was
designed and constructed. Tests were
carried out in a cylindrical reactor with a volume of 100 L with initial
pressures of 5 and 10 bar(a). The effect of the reacto
r adjustment (vertical or horizontal) was taken into
account. The current work describes the test set
up and summarizes the experimental results achieved.
Furthermore, this paper reports on a numerical model for
the prediction of the self
-heating of TFE in closed
vessels, which was previously developed for small scale reactors and has been here validated for larger
dimensions with the experiments performed in the new facility.
COMSOL Multiphysics® was used as a tool for the better understanding of the evolution of flow patterns during the induced ignition of gases. A simplified model was developed for the scope, by coupling the weakly compressible Navier Stokes module and the convection and conduction module. The current paper presents the results of the performed simulations.
Beim begehrten Kunststoff Teflon führt kein Weg an einem komplexen Herstellungsprozess vorbei, der aufgrund der besonderen Eigenschaften des Ausgangsstoffes spezieller sicherheitstechnischer Anforderungen bedarf.
Comsol Multiphysics unterstützte Wissenschaftler in der Auslegung der Produktionsanlagen bei der Identifizierung von Gefahrenquellen.
Preventing the explosion of acetylene cylinders involved in fire with help of numerical modeling
(2012)
The current paper describes a mathematical model, which was developed to simulate the heat transfer in acetylene cylinders during exposure to a fire. The cases of a direct engulfment of the cylinder in the flames and of exposure to a distant fire were considered. Furthermore, the model was also applied to the prediction of the heat transfer during the cooling with water of heated acetylene cylinders, in order to assess the effectiveness of this procedure as a measure to prevent the burst of the cylinder. To provide data for the definition and validation of the model a total of 13 bonfire tests with 8.9-, 10- and 50-dm³-cylinders were performed, where pressure and temperature measurements in the samples were performed. During 5 experiments the fire was extinguished before the expected cylinder burst and a cooling with water was applied. In the paper a short description of the experimental set-up and of the test results is given. Finally, a comparison with the model predictions is provided, showing reasonable agreement.
The Minimum Ignition Temperature of Decomposition (MITD) of tetrafluoroethylene in a partially heated pipe was analyzed for different initial pressures (5, 10 and 15 bara). The pipe used had an internal length of 1 m, an internal diameter of 30 mm with a volume of about 0.7 dm³ and was vertically oriented. Pressure at the pipe top and temperature at four different locations along the pipe axis were measured. Tetrafluoroethylene was found to decompose at lower temperatures for increasing initial pressures, in agreement with previous tests with reactors with fully heated walls. A complete passive quenching in the non-heated part of the pipe was observed only for an initial pressure of 5 bara, while for higher initial pressures, the decomposition propagated completely along the test pipe. Moreover, the test results on the MITD were compared with data from previous experiments in fully heated 0.2 and 3 dm³ cylindrical reactors and showed a decrease of the MITD with the heated volume through heated surface ratio of the vessel. Furthermore, the prediction of the MITD of tetrafluoroethylene by simplified calculation methods was attempted, showing a good agreement with the experimental results.
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.
Acetylenflaschen im Feuer
(2012)
Acetylen ist eines der wichtigsten technischen Gase und findet insbesondere Anwendung beim Schweißen und Schneiden verschiedener Werkstoffe. Damit Acetylen in entsprechenden Mengen vor Ort zur Verfügung gestellt werden kann, wird es in Druckgasbehälter abgefüllt. Im Falle eines Brandes stehen Acetylenflaschen im Verdacht, jederzeit – auch nach Löschen des Feuers – aufgrund einer möglicherweise initiierten Zerfallsreaktion zu bersten. Um insbesondere Personenschäden zu vermeiden, evakuieren und sperren die Rettungskräfte einen Sicherheitsbereich mit einem Radius von mindestens 200 m um die verdächtige Flasche ab. Gleichzeitig wird umgehend mit der Kühlung der Flasche begonnen. Wie lange muss aber eine Acetylenflasche gekühlt werden, bis sie sicher abtransportiert werden kann, und wie lange muss der Sicherheitsbereich mit dem großen Radius aufrecht erhalten werden? Diesen Fragen ist die BAM in den vergangenen Jahren im Rahmen verschiedener Untersuchungen und Projekte nachgegangen.
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.
Zur Einschätzung der Wirksamkeit einer heißen Oberfläche als Zündquelle für ein Gas oder ein Gasgemisch werden in der Praxis Zündtemperaturen experimentell bestimmt. Die Zündtemperatur gemäß dem europäischen Standardverfahren EN 14522 wird bei Atmosphärendruck bestimmt und ist vor allem dazu geeignet die Wirksamkeit einer heißen Oberfläche als Zündquelle bei einem unerwünschten Stoffaustritt aus einer geschlossenen Anlage einzuschätzen. Eine Aussage bzgl. der der Zündfähigkeit an heißen Oberflächen innerhalb einer geschlossenen Anlage, z. B. in größeren Behältern bei bestimmten Gemischzusammensetzungen und höheren Anfangsdrücken, kann anhand der Zündtemperatur gemäß EN 14522 nicht getroffen werden. Die Bestimmung nach dem europäischen Standard erfolgt in einem offenen System, bei atmosphärischem Druck und in Luft als Oxidationsmittel.
A mathematical model to predict the heating-up in open air wood chip piles has been developed. This model includes the heat production from chemical, physical and microbial exothermal processes. In the manuscript the laboratory experiments needed to develop and validate the model are described. In addition, temperature and gas concentrations were measured in two large-scale wood piles (volumes bigger than 1000 m³), in order to provide the applicability of the model to large-scale scenarios. The predictions of the model and the large-scale experimental data showed good agreement concerning the maximum temperature reached inside an open air wood pile. Special attention has been devoted to the microbial processes, since they proved to be the most important cause of heat production in the early stages of storage. This work is intended to help in predicting and thus avoiding possible self-ignition scenarios for this type of wood storage.
In this paper two different approaches for predicting the heating-up of an acetylene cylinder involved in a fire and the afterward cooling with water are presented. In the simulations polynomial functions were used to describe the temperature dependency of the thermal properties of the cylinder interior, which is a complex system composed by a solid porous material, a solvent (typically acetone) and acetylene dissolved in it. Model equations covered heat conduction in the cylinder interior and at its walls. In the first approach the cylinder surroundings were simulated as a further domain constituted by CO2, during the fire exposure, and for water, during the cooling. In this domain the coupled heat transfer (convection and conduction) and the momentum equation (Navier-Stokes) were solved. In the second approach no further domain was considered but boundary conditions were set directly on the cylinder walls. Results of the calculations performed with both approaches are presented. This work could prove helpful in predicting to which extent the interior of an acetylene cylinder exposed to fire reaches temperatures capable of initiating the decomposition of acetylene and to determine how long a water cooling should be applied, so that the system is brought again under non-critical conditions.
The temperature and gas concentrations in a
newly established pine-wood debris pile of 20 m × 15 m ×
6 m in dimensions (approximately 400 tons of fresh weight
material) were monitored for 150 days. Temperature was
measured at ten different positions within the pile, while
concentrations of CO2, O2, CO and CH4 were taken at four
different representative locations. The pile was characterized
by a strong temperature increase within the first 10–
12 days of storage. Results of the gas analysis in this period
suggest that the temperature increase was caused by microbial
processes. In particular, reduced oxygen concentration
and almost complete absence of methane indicate mainly
aerobic respiration processes. Effects of weather conditions
on the temperature/gas distribution and time evolution are
also discussed in the paper.
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.
There is a lack of data on the self-ignition behaviour of tetrafluoroethylene in industrial sized equipment. Therefore, a facility was designed and constructed for the determination of the Minimum Ignition Temperature of Decomposition of tetrafluoroethylene in a cylindrical reactor with a volume of 100 dm3. Tests with initial pressures of 5 and 10 bar(a) were performed. The Minimum Ignition Temperature of Decomposition of tetrafluoroethylene was observed to decrease with the initial pressure, in agreement with previous experiments with small scale cylindrical vessels. This paper describes the test set-up und gives an overview of the achieved experimental results. In particular the effect of the reactor orientation (vertical or horizontal) is discussed. Furthermore, simplified equations from the Semenov thermal explosion theory are used to attempt extrapolations of previous and current data on the Minimum Ignition Temperature of Decomposition of tetrafluoroethylene to other vessel volumes or initial pressures. Moreover, the experimental data are plotted together against the heated volume to heated surface ratio, which should provide a better extrapolation to other vessel dimensions by taking into account that the efficiency of the dispersion of the heat generated by the reaction is different for two reactors with the same volume but different diameter. Finally, simplified methods for predicting the Minimum Ignition Temperature of Decomposition of tetrafluoroethylene presented previously by the authors are validated for large scale reactors with the experimental data collected within the current work.
In the industry there is a lack of data on the Minimum Ignition Temperature of decomposition of tetrafluoroethylene in industrial sized equipment. In order to determine the Minimum Ignition Temperature of Decomposition of tetrafluoroethylene in large scale vessels, a facility was designed and constructed. Tests were carried out in a cylindrical reactor with a volume of 100 dm³ with initial pressures of 5 and 10 bar(a). In agreement with previous experiments with small scale cylindrical vessels, the Minimum Ignition Temperature of Decomposition of tetrafluoroethylene was observed to decrease with the initial pressure. The current paper describes the test setup and summarizes the experimental results achieved. The effect of the reactor adjustment (vertical or horizontal) is discussed. Moreover, simplified equations from the Semenov thermal explosion theory are used to attempt extrapolations of previous and current data on the Minimum Ignition Temperature of Decomposition of tetrafluoroethylene to other initial pressures and vessel volumes.
Die adiabate Kompression stellt insbesondere für zerfallsfähige Gase eine potentielle Zündquelle sowohl bei Herstellungsprozessen als auch beim Umgang in weiterverarbeitenden Betrieben oder beim Endnutzer dar. So kam es in der Vergangenheit etwa in TFE-verarbeitenden Anlagen wiederholt zu Störfällen durch Adiabate Kompressionsvorgänge des Monomers. Unter dem Begriff „zerfallsfähige Gase“ oder auch „chemisch-instabile Gase“ versteht man Gase, bei denen es auch in Abwesenheit eines Oxidators nach einer Zündung zu einem explosionsartigem Reaktionsverlauf kommen kann, wie es etwa beim Tetrafluorethylen (TFE) der Fall ist.
Die Zerfallsreaktion von TFE ist in Gleichung dargestellt. Sobald eine Zündquelle die Zerfallsreaktion initiiert, kann diese bei bestimmten Anfangsbedingungen von Druck und Temperatur explosionsartig verlaufen. Die schnelle Reaktionsrate zusammen mit der hohen Exothermie der Reaktion kann zur Bildung von heftigen Explosionen führen, wie sie sonst nur bei Brenngas/Oxidator-Gernischen üblich sind.
Fast growing softwood species such as pine are preferred for biomass-based heat as well as electricity production and stored in large quantities. A newly established outdoor pile of freshly cut pine-wood chips was monitored to analyze exothermic processes. Inside the pile, a mean temperature increase of up to 44 °C was measured after six days of piling which was paralleled by a decrease of O2-concentration and an increase of CO2-concentration. Thereafter four additional CO2 maxima were observed, while O2-concentration remained at ambient concentration. The fungal community structure remained almost unchanged after four weeks, while the bacterial community structure was characterized by continuous shifts over time. The rapid heating in the early stage of storage corresponded to high relative abundance of microbial strains belonging to the genera Pseudomonas, Luteibacter and Caulobacter, ascomycetous genera Sphaeropsis and Cadophora and basidiomycetous order Polyporales and genus Sistotremastrum. The late stage was composed by a broader diversity of microorganisms, and heating processes inside the wood pile were attributed mainly to physicochemical processes. Taken together, these observations suggest that the early bacterial and fungal communities are key players in exothermic processes and were replaced by a broader diversity of highly adapted microorganisms.
Fire exposure tests of acetylene cylinders were performed. The purpose of the experiments was to gather information on the behavior in fire of such vessels, depending on the initial charge of acetylene. In fact "empty" acetylene cylinders still contain the solvent in which acetylene is dissolved plus the amount of acetylene to saturation at atmospheric pressure and ambient temperature and may still constitute a threat to safety. In the fire exposure tests performed the hazardousness of these vessels was demonstrated, since it was observed that not only fully charged acetylene cylinders but also cylinders with saturated solvent can explode, provided the heat transfer to the vessel is sufficient. The times to explosion were shorter for fully charged cylinders, due to the higher initial pressure and to the faster pressure increase. The effects of the explosions are comparable for both fully charged cylinders and for cylinders with saturated solvent, except for the smaller fireball which is produced in the second case, due to the smaller amount of fuel available. In both cases the cylinder walls or at least fragments can fly further than 100 m away from the burst location. Results of the experiments are presented in the paper. During the tests, temperature measurements at the cylinder walls and in the cylinder interior were performed. Furthermore, the pressure in the cylinder was recorded. The collected data will serve for the validation of a numerical model for the simulation of the heating of acetylene cylinders involved in fire and of the afterward cooling with water, which has been developed. The constitutive model equations and the results of some simulations are presented in the paper.
In order to prevent incidents in the
industrial production of Teflon® from
Tetrafluoroethylene (TFE), the safety related
aspects of the self-heating process of TFE must
be taken into account. Simulations of this self
heating process were performed with COMSOL
Reaction Engineering Lab® and COMSOL®
COMSOL Multiphysics®. A complex reaction
net was employed, resulting in a model allows
for a good agreement with experimentally
achieved results.
Prevention of the explosion of acetylene cylinders involved in fire: experiments and simulations
(2011)
In order to assess the effectiveness of water cooling of acetylene cylinders involved in fire, a total of 13 bonfire tests with 8.9-, 10
and 50-l-cylinders were performed. During the experiments the pressure
in the cylinder and the temperature at different locations within the porous material and on the Shell surface as well as the flame temperature were measured. Overall 8 burst tests were performed, in order to determine the times to explosion for the cylinders. Cylinders failed not later than 15 minutes from the ignition of the bonfire, often with generation of a fireball. During the other 5 tests, the fire was extinguished before the expected burst and the cylinder was cooled with water. In 2 of the 5 extinction experiments, the explosion of the cylinder could be prevented. Noticeably, in one case the on-set of the decomposition of acetylene had already been observed, before the cooling was started. In spite of that, the cooling was still effective. The interpretation of the current results and of the data from previous tests with 40-l-cylinder suggests that single acetylene cylinders involved in fire might be saved by cooling, if their pressure does not exceed a value of about 45 bara. The recorded values of pressure and temperature were used to develop and validate a mathematical model for the prediction of the heat transfer in acetylene cylinders during the exposure to fire and the afterward cooling. The predictions agreed well with the experimental results.
Prevention of the explosion of acetylene cylinders involved in fire: experiments and simulations
(2011)
Das Interesse für erneuerbare Energieträger ist in den letzten Jahren stark angestiegen.
Im Bereich Biomasse als erneuerbarer Energieträger wird besonders Holz ein großes
Wachstum auf dem Energiesektor prognostiziert (NITSCH 2007). Die Speicherung dieser
Energie erfolgt meist durch Holzhackschnitzelhalden in der Umwelt. Um ein tieferes Verständnis
der in der Halde ablaufenden mikrobiologischen Prozesse erhalten zu können,
wurden in einer neu aufgebauten Kiefernholzhackschnitzelhalde mit den Ausmaßen
15 m x 20 m x 6 m folgende Messungen durchgeführt: a.) Messung der Gaskonzentration
von Sauerstoff, Kohlendioxid als auch der Temperaturentwicklung innerhalb der Halde; b.)
Messung der Veränderung der Holzzusammensetzung innerhalb der Halde über die Zeit;
c.) Charakterisierung der Veränderung der Zusammensetzung der bakteriellen als auch
der pilzlichen Lebensgemeinschaften über die Zeit; d.) Charakterisierung von dominanten
Vertretern der bakteriellen als auch der pilzlichen Lebensgemeinschaften. Die Ergebnisse
zeigen, dass sich die Funktion und die Zusammensetzung der Lebensgemeinschaften
über die Dauer der Holzhackschnitzellagerung ändern, und dass diese Änderungen nur
zum Teil mit den Prozessen bei Kompostierungsanlagen vergleichbar sind.
In this paper a mathematical model for predicting the heating-up of an acetylene cylinder involved in a fire is presented. In the simulations polynomial functions were used to describe the temperature dependency of the thermal properties of the cylinder interior, which is a complex system composed by a solid porous material, a solvent and acetylene dissolved in it. Model equations covered heat conduction in the cylinder interior and at its walls, while the fire surrounding the cylinder was simulated by solving the coupled heat transfer and the momentum equation. Results of the calculations and the effects of some model parameters are discussed.