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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.
Data and prediction for the mass burning rate of a tert-butyl-peroxy-benzoat (TBPB) pool fire (pool diameter = 3 m) is presented. The mass burning rates of TBPB fires are up to six times higher and less dependent on pool diameter compared to hydrocarbon pool fires caused by an additional heat release rate due to exothermic decomposition reaction in the liquid phase. This heat release rate is calculated using a 1st order reaction kinetic obtained from micro calorimetric measurements. A new model is derived considering the heat release rate due to the decomposition reaction which is shown to be 100 % of the heat release rate radiated to the pool surface. With the presented model, including also physical quantities, especially the limiting fuel concentration for upward flame propagation, it is possible to predict the mass burning rates of large TBPB pool fires. The predicted values are in very good agreement with the experiments.
The diffusive burning characteristics of four peroxy-fuels (usually known as liquid organic peroxides) and one hydrocarbon fuel are experimentally investigated targeting alternative fuels (or as additives to conventional fuels) for the future. Measurements are performed in form of pool fires with pool diameters in the range between 1 cm and 1 m. Mass, momentum and energy transfer studies are carried out by measuring the mass burning rate, flame length, flame temperature and radiation heat transfer across the liquid fuel and gaseous flame. It has been shown that comparatively much less mass of peroxy-fuels and pressure drop (required to maintained the flow) of fuel are required to produce a given heat flux. The momentum delivered by the peroxy-fuel vapours are order of magnitude higher than for hydrocarbons making the visibility of flame to be 4–5 times larger. A heat balance analysis shows that the total heat release rate of a peroxy-fuel fire is contributed equally by convection and radiation. Finally, the three E's (Efficiency, Economy and Emission) are discussed in the context of present experimental results followed by some recommendations concerning safe handling of the proposed fuels.
IGUS is the International Group of Experts on the Explosion Risks of Unstable Substances. Today, the aim of the group is to exchange information on the behavior of unstable substances and to improve safety in production, storage, transport, and use of these substances. Full members of IGUS work for governments and independent research organizations. Experts from industry can and do attend meetings by invitation. IGUS's 50th anniversary in 2012 gives reason to have a closer look at the questions of how IGUS came to be, what IGUS's aims and objectives were, and how it is organized and working today.
Industrial fire and explosion hazards due to accidents in fuel storage units have gained a
considerable attention in the recent times. Both the regulatory bodies and scientific communities
are heavily concerned about the proper safety measures to avoid such calamities in future. This
paper aims to bring some essentials related to the hazards arose from the recent fuel storage fire
accident occurred in Buncefield, UK (2005), Puerto Rico, USA (2009) and Sitapura, India (2009).
The potential similarities behind occurrence of these accidents are studied. The applicability of
various methods (models) and also computer simulations to estimate the safety distances
according to the international standards for both explosion and fire hazard are verified. The
overpressures caused by the Vapor Cloud Explosion (VCE) and radiation flux emitted by the fire
are considered for respective explosion and fire hazard estimations. The prime focus is placed
on the regulations laid down by the National Fire Protection Agency of the United States and
the European Norms.
IGUS is the International Group of Experts on the Explosion Risks of Unstable Substances. IGUS was established in 1962 with the objective to harmonize test methods used by different countries to identify and quantify the explosive properties of unstable materials. Over the years, IGUS has continued to offer scientists, who are advisers to their governments, and others, a forum to exchange data and information. The Energetic and Oxidizing Substances (EOS) working group as a sub-group of IGUS is dealing with test methods, Classification and safety aspects relating to organic peroxides, self-reactive substances and other energetic substances, fertilizers, ammonium nitrate and oxidizers.
The EOS working group holds an annual meeting alternating between Europe, the United States and Japan. The 2011 meeting took place from the 27th to the 29th of April 2011 at the Madison Hotel in Washington, D. C. The meeting was hosted by the Organic Peroxide Producers Safety Division (OPPSD) of the Society of Plastics Industry, Inc. (SPI). This was the fourth EOS meeting held in the USA since 1994. Of particular importance is the fact that 39 colleagues from authorities, universities, research institutes and industries attended the meeting. The delegates came from USA, Canada, China, France, The Netherlands, Norway, Sweden, Italy, Japan, United Kingdom and Germany. This confirms the breadth and scope of this forum and the value the participants associate with being able to contact other colleagues from around the world enabling the effective exchange of scientific results and discussion on the wide-ranging Problems concerning energetic and oxidizing materials.
Data and predictions for the mass burning rates of di-tert-butyl peroxide (DTBP) pool fires (0.003 m < pool diameter < 3 m) are presented. The mass burning rates of DTBP fires are up to five times higher and are less dependent on pool diameter compared to hydrocarbon pool fires caused by an additional heat release rate due to exothermic decomposition reaction in the liquid phase. This heat release rate is calculated using a first-order reaction kinetic obtained from microcalorimetric measurements. A new model is derived considering the heat release rate due to the decomposition reaction, which is shown to be 40% of the heat release rate radiated to the pool surface. With the presented model, which also includes physical quantities, especially the limiting fuel concentration for upward flame propagation, it is possible to predict the mass burning rates of large DTBP pool fires. The predicted values are in very good agreement with the experiments.
Es werden Experimente zur Bestimmung der Massenabbrandraten von multiplen Poolfeuern präsentiert. Als Modellsubstanzen dienen n-Heptan und Di-tert-butylperoxid (DTBP). Es werden Versuche im Labormaßstab mit Durchmessern von d = 6 cm und relativen Abständen von 0.08 ≤ D/d ≤ 4 beschrieben und durch Feldversuche mit Pooldurchmessern d = 1.5 m und relativen Abständen zwischen den Pool von 0.17 ≤ D/d ≤ 1 ergänzt. Es kann gezeigt werden, dass die Massenabbrandraten multipler Feuer im Vergleich zu Einzelfeuern mit gleicher Brennstoffoberfläche bis zu einem Faktor 5.9 (n-Heptan) und 1.6 (DTBP) erhöht sind. Die Erhöhung ist abhängig vom relativen Abstand zwischen den Pools D, der Anzahl der Pools N und vom jeweiligen Brennstoff und zeigt ein lokales Maximum, welches mit dem Merging-Bereich der Flammenverschmelzung zusammenfällt. Die Massenabbrandrate als Funktion des relativen Abstandes zwischen den Pools kann durch eine Vergrößerung der Flammenbodenoberfläche infolge Flammenverschmelzung erklärt werden.
Present work deals with the potential usage of peroxy-fuels (usually known as organic peroxides) in engine combustion processes. Although as additives (in small quantities < 5% to conventional fuels e.g. diesel, gasoline) peroxy-fuels are well known for many years their commercial applications as a main or primary fuel are not investigated in detail as such except a few. Since they are thermally unstable and energetic their safety demands great care during processing which restricts their commercial exploitation. However, once the issues with safety are resolved they can be much more advantageously employed than conventional fuels. Some of these advantages are: significant amount of fuel saving, reduction in amount of inducted air or even in the complete absence of air i.e. anaerobically, smaller volume of combustion (chamber), oxygenated fuel quality and low emissions. In this study we introduce an idea to develop the components of an engine operating solely on peroxy-fuels. The engine concept is based on single and multiple injectors in a cylinder with special material coating to ensure a temperature controlled processing.
Limiting distances for flame merging of multiple n-heptane and di-tert-butyl peroxide pool fires
(2013)
Experiments to determine the limiting distances for flame merging of multiple pool fires are presented. As model substances n-heptane and di-tert-butyl peroxide are used. Laboratory scale tests with a Diameter d = 6 cm and relative distances between the pools of 0.08 ≤ D/d ≤ 4 are described and complemented with field experiments with a diameter d = 1.5 m and relative distances between the pools of 0.17 ≤ D/d ≤ 1.
Three regions for flame merging are observed and limiting distances are determined. A merging Region with the limiting distance Dmerg/d within which all flames merge together over the complete burning time. A transition region with the limiting distance Dtran/d within which some flames merge together while other flames are separated from each other. A separated region within which all flames are completely separated from each other. A correlation against the number of burning pools is presented to predict the limiting distances Dmerg/d und Dtran/d.
Most of the measurements of temperatures in large pool fires are indirect and present a number of complexities due to the interactions of convection, radiation and soot blockage. In the present work these influences for two organic peroxide [tert-butyl peroxybenzoate (TBPB) and tert-butyl peroxy-2-ethylhexanoate (TBPEH)] pool fires are analysed.
Thermocouple measured temperature in the clear flame zone i.e. combustion zone are found to be 250-400 K lower than from the thermographic measurements. The convective and radiative heat flux contributions from the fire on temperature measurements are discussed. CFD (Computational Fluid Dynamics) simulations have been performed for large pool fires and the predicted time averaged flame temperatures were found to be in qualitative agreement with
measurements due to the stoichiometric combustion model used in the present simulations.
Flame temperature (T), surface emissive power (SEP) of Liquefied Natural Gas (LNG) pool fires (d = 1 m, 6.1 m, 30 m) are investigated by CFD (Computational Fluid Dynamics) simulation and compared with experimental results.
Time averaged flame temperatures of T = 1320 K, T = 1298 K and T = 1281 K are obtained. Surface emissive power (SEP) of 55 kW=m2, 130 kW=m2 and 230 kW=m2 are predicted.
The use of energetic materials as a main fuel in high temperature process
industries are not known to the scientific community as such. This paper
highlights some of the features and advantages of using organic peroxides
especially di-tert-butyl peroxide (DTBP) in high temperature process industries.
The feasibility of using DTBP as a main or supporting fuel in process industries
have also been justified with the help of Computational Fluid Dynamics (CFD)
simulations. For peroxides requirement of less fuel and air for the same amount
of heat flux has been shown. The resulted emission from the combustion of
DTBP is also discussed.
Combustion of peroxy-fuels
(2011)
The diffusion flames of organic peroxides exhibit quite different characteristics than hydrocarbons. What makes them interesting to study is their fast burning behaviour. As a result the flame temperature enhances and so does the thermal radiation. Due to all these they demand safe handling during processing. However, they can be utilised at several places in different industries where a fuel with fast burning, high temperature and intense radiation are desired. Some of the possibilities to use them as a main or supporting fuel in a wide range of industrial utilities are the major content of this paper.
A new burner concept (PEROXY-BAM®) for the combustion of liquid organic peroxides (Peroxy-fuels) is presented. As peroxy-fuels are thermally unstable the design of burners for them should be accordingly modified ensuring a safe operation. It is found that 10 to 100 time less amounts of peroxy fuels are required for the same heat flux or output in comparison to hydrocarbons. Correspondingly, the fuel pump power and the volume of combustion chamber (furnace) are also reduced. As a result of less amount of fuel the emissions will also be stepped down and oxygen in the molecule helps to establish conditons like in an oxy-fuel combustion process. The advantages of using peroxy-fuels over hydrocarbons inside a model combustion chamber are also investigated with the help of CFD (Computational Fluid Dynamics) simulations.