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Eingeladener Vortrag
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Massenabbrandraten organischer Peroxide unter besonderer Berücksichtigung der thermischen Stabilität
(2013)
Die Flüssigkeitstemperatur Temperatur in der flüssigen Phase unmittelbar im Grenzbereich zur Gasphase während eines Abbrandes organischer Peroxide überschreitet die Onset-Temperatur der beginnenden exothermen Zersetzungsreaktion des Peroxids, so dass diese zu berücksichtigen ist. Für die Peroxide Di-tert-butyl-Peroxid (DTBP) und tert-butyl-peroxybenzoat (TBPB) muss daher bei der Berechnung des Wärmerückstromes ein zusätzlicher Term für die Zersetzung in der Flüssigkeit additiv ergänzt werden. Der Umsatz der Zersetzungsreaktion wird unter den Bedingungen eines CSTR modelliert und erfolgt auf Basis einer Reaktionskinetik 1. Ordnung. Es kann gezeigt werden, dass der Wärmestrom in einem DTBP-Poolfeuer ≈ 40 % und einem TBPB-Poolfeuer ≈ 100 % des Wärmerückstromes durch Wärmestrahlung entspricht. Durch Q-Punkt-d können die vergleichsweise hohen Massenabbrandraten und die relative Unabhängigkeit der Massenabbrandraten vom Pooldurchmesser erklärt werden. Über eine Energiebilanz wird ein Modell basierend auf physikalischen Parametern entwickelt, das die Massenabbrandraten großer Poolfeuer, in sehr guter Übereinstimmung mit den experimentellen Ergebnissen, vorhersagt.
Amuay refinery disaster (2012) is another recent example of Vapor Cloud Explosion (VCE) and fire accidents preceded by Buncefield (2005), Puerto-Rico (2009) and Jaipur (2009), respectively [9]. The incident has left many safety issues behind which must be repeatedly addressed. Unfortunately, the lessons taught by previous similar events are just not understood carefully. It reveals that the proper safety measures for such facilities were either underestimated or were not accounted seriously. Consequently, the resulting overpressures from explosion and the subsequent thermal radiation from tank fires have once again proved to be disastrous to both mankind and infrastructure. This article highlights the aftermaths of Amuay incident and addresses the challenges put forward by it. Furthermore, a comparative study is performed between such incidents to analyze the similarities and how they could have been avoided.
Dampening of energetic properties and the effects of blending proportions of isododecane on the diffusive burning behaviour of peroxy-fuels are experimentally studied. Blended peorxy-fuels are obtained by adding isododecane in the proportions of 25 wt.%, 50 wt.% and 75 wt.%, respectively, in technical pure peroxy-fuels. The fuels were burned in form of pool fires with diameters 0.02 m ≤ d ≤ 1 m. The mass burning rates and relative flame lengths are found to be weakened with increasing diluent proportions. By measuring the mass burning rates and visible flame lengths of pool fires of different samples of fuel blends an optimum blending criterion is developed. Furthermore, it is shown that the dilution proportions and flame characteristics can be correlated by empirical equations.
Two-phase CFD (Computational Fluid Dynamics) model for characterising the spill-over/dispersion of peroxy-fuels is presented. The model is independent of type and burning rate of the spilled/dispersed fuel and considers only overflow Reynolds number (Re) to characterise the spill/dispersion behaviour. Additional simulations are performed for LNG (Liquified Natural Gas) dispersion and it is found that the model can be used for different fuels within a defined range of Re. Different scenarios with Re = 100 to 3 × 105 are investigated covering a wide range of mass flow rates, opening sizes and viscosities. Depending on Lower Flammability Limits (LFL) of the fuels spill/dispersion (vapour cloud) diameters (DCFD) and heights (hCFD) are predicted. A generalised correlation between DCFD and Re is established to predict the dispersion occurring at varying scales. The model is validated by: (1) conducting an extensive grid independent study; (2) comparing the results with the existing analytical methods and (3) comparing against the standard field test data on LNG dispersions.
Industrial fire and explosion hazards are most often also associated with the dispersion of toxic substances.
These substances can be gases, liquids, solids or in form of aerosols. The critical toxic exposure limits to People and enviroment from such substances are regulated by the concerned authorities of the countries. In order to comply with the defined regulation estimation of such critical limits must be carried out by different semi-empirical and phenomenological models/methods for risk assessment.
Many of such methods provide a qualitative estimation of time and space dependent extrimities of toxicity. The overwhelm development of computational capacity has made it possible to perform Computational Fluid Dynamics (CFD) simulation by solving the three-dimensional transport equations for mass momentum and species in lower and upper atmosphere, respectively. CFD simulation not only provides a detailed 3D distribution of toxic particulates/gases in the neighbourhood of the plant but also helps to study the worst-case sceanrios. In the past several small- and large-scale accidents occured in oil and gas plants in different parts of the world including the recent one in Rheinland refinery near Cologne in Germany. This work deals with this accident and provides a methodology to predict the critical exposure limits of smoke emitted by a toluene tank fire by means of CFD simulation.
Organic peroxides are energetic substances liable to decompose due to exothermic reactions when exposed to uncontrolled temperature, contamination, confinement and quantity. Their safe storage and transportation are the prime concern and chemical industries and regulating authorities. Their accidental release may and most often lead to shape of a pool. In present study, safety distances from such large pool fires (diameter d = 3.4 m) of organic peroxides are numerically predicted by solving the reactive, 3-D time dependent Navier-Stokes equations with reliable assumptions. The present model is validated against the data on buoyant turbulent diffusion flames. The safety distances predicted by simulation assume three regions in a fully developed fire i.e. hot spot, luminous zone and a flame surface. The time averaged data of temperatures of these regions lead to better estimation of irradiances against the measured data. A developed sphere analogy method (for a special class of organic peroxides) for maximum surface emissive power prediction is also verified.
The industrial fire accidents e.g. Buncefield (2005) and Jaipur (2009) have come up with several issues concerning safe storage and transportation of flammable liquids. The pre and post fire consequences are therefore important to be analyzed prior to the handling of flammable fuels. Pool or/and tank fire is the most often seen scenario after the leak/spill of liquid fuel. An overview of the typical scenarios from large hydrocarbon and organic peroxide pool fires and their respective safety distances for the people and the infrastructure are the important subjects of this paper.
Combustion of peroxy-fuels
(2011)
Die thermische Zersetzung von AIBN wurde in einem Projekt mit mehreren Teilnehmern untersucht. Hierbei wurde die selbstbeschleunigende Zersetzungstemperatur SADT) sowohl experimentell als auf Grundlage von Simulationsrechnungen bestimmt. Die Besonderheit bei dem Feststoff AIBN ist, dass die Zersetzung sowohl in der festen, als auch in der flüssigen Phase nach dem Schmelzen stattfindet, was bei den durchgeführten Simulationsrechnungen berücksichtigt werden musste. Die berechneten SADT Werte stimmen mit den experimentell bestimmten sehr gut überein.
Das Abbrandverhalten und die thermische Strahlung von Poolfeuern organischer Peroxide (OP) wurden bereits in der Vergangenheit ausführlich untersucht. Dabei ergaben sich zum Teil erhebliche Unterschiede hinsichtlich der Abbrandraten, Temperaturen, Strahlungsintensitäten und Flammenlängen im Vergleich zu flüssigen Kohlenwasserstoffen. Das größere Gefahrenpotenzial von OP führt zu strikteren Sicherheitsbestimmungen für Lagerung und Transport. Da das Gefahrenpotenzial maßgeblich von den tatsächlich auftretenden Szenarien abhängt, ist eine Bewertung solcher Ereignisse unumgänglich um nachhaltig die Gesundheit von Mensch und Umgebung zu sichern. Ein Metallfass, gefüllt mit 200 Litern DTBP (Di-tertiär-butylperoxid), wurde auf dem Testgelände Technische Sicherheit der BAM einem Außenfeuer ausgesetzt. Durch den starken Wärmeeintrag erhöht sich die Massenabbrandrate des Peroxids um ein Vielfaches und das Fass entleert sich schließlich unter Ausbildung mehrerer Feuerbälle. Die Flammengröße, Flammentemperatur und damit die thermische Strahlung überschreiten die der gewöhnlichen OP-Poolfeuer. Die resultierenden höheren Sicherheitsabstände sind abschließend berechnet.
Fire and explosion hazards associated with storage and transportation of flammable materials have been a matter of great interest in the recent times. BLEVE is a scenario that occurs when a closed fuel container is subjected to heat for a longer duration. Such events are disastrous to human beings and assets both. In the past there have been numerous studies on BLEVEs and fireballs of hydrocarbon fuels, e.g. kerosene, gasoline, LPG, LNG and others. Though, the fireballs of peroxy-fuels are not looked into detail as such. This article tries to overcome this lack of knowledge. Both, experimental investigation and CFD simulations are performed to measure and predict the fireball characteristics of a peroxy-fuel. Due to thermal decomposition in the liquid phase and active oxygen content a peroxy-fuel fireball burns at a very fast rate and emit higher thermal radiation whereas exhibits smaller diameter and elevation compared to hydrocarbons. That eventually leads to consideration of larger safety distances from them which are also verified by CFD results.
Scenarios of underground gas pipeline failure, crater formation, dispersion of gas, explosion and subsequent fires are investigated with semi-empirical and with CFD (Computational Fluid Dynamics) modelling. In order to strengthen the accident based learning approaches present investigations are performed in the context of recent GAIL (Gas Authority of India Limited) natural gas pipeline incident occurred in India. The foreseeability of damages to lives of people and assets due to explosion overpressure and thermal radiation are assessed. The released gas is considered as slightly dense-than-air i.e. 1.5 times. Depending on the LFL (Lower Flammability Limit) of gas the dispersion diameter and heights are predicted which followed the visual evidences appropriately. The model was furthermore tested with an even denser medium and was found to be worked well there too. The estimated explosion overpressures with the standard methods and also with CFD reproduced the scenario nicely. The effects of congestion VBR (Volume Blockage Ratio) in form of vegetation on stable atmospheric boundary layer flow is analysed and its contribution towards turbulence and hazard enhancement is studied.
It is found that the major source of fatalities was higher thermal radiation emitted by pool fires of methane. The estimated thermal safety distances clearly demonstrate the ignorance/under estimation of likelihood and consequence of such hazardous events. For such incidents CFD demonstrated a strong capability to assess the pre or/and post events foreseeabilities within a reasonable amount of time and with an acceptable level of accuracy meeting the industrial needs for risk analysis.
CFD (Computational Fluid Dynamics) simulations have been carried out to investigate the behavior of turbulent, subsonic jet fires of the peroxy-fuel Di-tert-butyl peroxide (DTBP) using the SAS-SST turbulence model, the discrete transfer radiation model, the eddy dissipation combustion model and the Magnussen soot model. Safety relevant parameters, such as flame length, temperature and thermal radiation are predicted to give recommendations on safety distances.
A volumetric source based CFD (Computational Fluid Dynamics) model for estimating the wind and gravity driven spread of an elevated released dense hazardous cloud on a flat terrain without and with obstacles is demonstrated. The model considers the development of a worst-case scenario similar to that occurred at Bhopal. Fully developed clouds of a dense gas having different densities, under ABL (Atmospheric Boundary Layer) with calm ground wind conditions are first obtained. These clouds are then allowed to spread under ABL with different ground wind speeds and gravity conditions. The developed model is validated by performing the grid independent study, the fluid dynamical evidences, post-disaster facts, the downwind MIC (Methyl Isocynate) concentrations estimated by earlier models and experiments on dense plume trajectories. It is shown that in case of an active dispersion under calm wind conditions the lateral spread would prevail over the downwind spread. The presence of a dense medium behaves like a weak porous media and initiates turbulence at much smaller downwind distances than that normally would occur without the dense medium. The safety distances from toxic exposures of MIC are predicted by specifying an isosurface of a minimum concentration above the ground surface. Discrepancies in near-field predictions still exist. However, the far-field predictions agree well with data published before.