2.2 Prozesssimulation
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Eingeladener Vortrag
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The Globally Harmonized System of Classification and Labelling of Chemicals (UN-GHS) is being implemented in more and more countries all over the world; the EU has done so with the CLP-Regulation (EU-CLP). Compared to the undeniably important questions on health and environmental hazards, the classification of physical hazards of chemicals often has not been in the focus, although their implementation can be challenging and there are traps and pitfalls to be avoided. The following overview of the classification systematics for physical hazards aims at a principle understanding without detailing all criteria or test methods. Similarities and differences between the classification systems of the UN-GHS and EU-CLP, the transport of dangerous goods and the former EU system are reviewed with regard to the physical hazard classes. Available physical hazard classifications for the transport of dangerous goods and according to the former EU system can be used as available information when classifying according to the GHS. However, the interfaces of these classification systems and their limitations have to be understood well when concluding on GHS/CLP classifications. This applies not only to industry when applying CLP but especially to legislators when adapting legislation that in one way or another refers to the classification of chemicals.
One of the fundamental principles of the UN-GHS (Globally Harmonized System of Classification and Labelling of Chemicals) is that all hazards of a chemical should be assigned and communicated. There is no general prioritization of hazards in the sense that certain hazard classes are not applicable if another one has been assigned. In contrast to health and environmental hazards, there are physical or chemical factors which preclude certain combinations of physical hazard classes. So far, there is no common understanding as to which combinations are relevant and which not. For example, should a pyrophoric liquid be classified as flammable liquid in addition, or is this redundant and unnecessary? In the course of the implementation of the GHS by countries or sectors and the actual application by industry all over the world, such questions become more and more important. For many of the combinations an unambiguous decision based on theGHS alone is not possible, thus confirming that the question which physical hazard classes might be assigned simultaneously to a chemical is not trivial. As one more milestone on the path to a globally harmonized system for the classification of hazardous chemicals, this should be discussed and ultimately solved on a global basis. It is the hope that this presentaion might serve as an impetus for such discussions.
In present chapter, the potential usage of peroxy-fuels (usually known as organic peroxides) either in technically pure or in a blended form in engine combustion processes are explored. 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. Their thermal instability and energy density demand 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 the complete absence of air, i.e., anaerobic combustion, smaller volume of combustion (chamber), oxygenated fuel quality, and low emissions. An idea to develop the components of an engine operating solely on peroxy-fuels is also introduced. The engine concept is based on single and multiple injectors in a cylinder with special material coating to ensure a temperature-controlled processing.
Transposition of regulations of the (German) employer’s liability insurance association (BGV’n) into Federal responsibility.
Fundamentals are regulated in the German Hazardous Substances Ordinance (GefStoffV). Prospectively, some definitions and more details are specified in a Technical Rule (TRGS 741 „Organic Peroxides“). A second project outline was discussed in 2014; because of some formal objections concerning the process and, particularly, the membership in a project group, no progress et al. since 2014.
Nevertheless, the BGV B4 is still valid. Because of some new findings and new test results a revision and Supplementation of the table of assignments of OP to risk (storage) groups was required.
Summary of recent research activities at BAM concerning large scale fireballs of organic peroxides (OP). Videos of the tests performed in Nanjing, China, are presented. A new model for OP fireball diameter, duration, height and SEP is proposed based on all experiments. In addition, small scale test results using DTBP and heptane are presented. Finally, CFD simulation is used to predict the fireball parameters: diameter, duration and height.
The thermal radiation impact of organic peroxide fireballs is experimentally assessed using an infrared camera. Fireballs are generated while liquid peroxide filled steel drums are subjected to gas burner fire at different heating rates. Three large burning clouds are observed with varying flame characteristics. Thermal radiation properties are assessed by infrared images with the presented methods. Despite of the two-dimensional temperature fields, the flames are treated and characterized as three-dimensional objects. Fireball diameters and heights are calculated based on a representing radiating sphere with the same cloud volume. By the use of the solid flame model and assumptions for emissivity and transmissivity, heat fluxes and thermal radiation doses against distance are predicted. Thermal safety distances are presented based on the maximum irradiance and the allowed exposure time. The validation of the maximum and time-dependent radiation fields is achieved through heat flux sensors in varying distances to the fireball. The results prove the use of an infrared camera and a volume based size calculation to fully assess the thermal radiation hazards of fireballs.
Auswirkungen hoher thermischer Belastungen auf flüssige organische Peroxide in Metallbehältern
(2018)
Im Gegensatz zu thermisch instabilen Kunststoffverpackungen garantieren Metallbehälter auch bei hoher thermischer Belastung, beispielsweise durch ein Schadenfeuer, einen stetigen Wärmeeintrag. Ist ein flüssiges organisches Peroxid enthalten, wird durch die Wärme eine sich selbst-beschleunigende exotherme Zersetzung initiiert. Das mit der Entzündung der Zersetzungsgase entstehende Feuer brennt durch den kontinuierlichen äußeren Wärmeeintrag heftiger als dies bei Poolfeuern organischer Peroxide zu beobachten ist. Aufgrund des definierten Einschlusses einer Metallverpackung kann die Zersetzung explosionsartig ablaufen und zur Ausbildung ein- und mehrfacher Feuerbälle führen. Auswirkungsbetrachtungen eines mit flüssigem organischen Peroxid befüllten und von außen befeuerten 220 Liter Stahlfasses wurden anhand zahlreicher Versuche mit unterschiedlichen Aufheizmethoden durchgeführt und sowohl die ermittelten Abbrandraten als auch die gemessenen thermischen Strahlungsbelastungen mit denen eines Poolfeuers verglichen. Die Analyse des Gefahrenpotentials unterschiedlich großer Feuerbälle führte schließlich zur Entwicklung eines ersten semi-empirischen Modells zur Abschätzung des Durchmessers und der Abbranddauer von Feuerbällen organischer Peroxide. Daraus ergibt sich die Möglichkeit der Berechnung notwendiger thermischer Sicherheitsabstände.
Biozidprodukte unterliegen einer Zulassungspflicht, bevor sie verkauft oder angewendet werden dürfen. Zulassungsanträgen für Biozidproduktfamilien sowie für in-situ-Systeme müssen als IUCLID-Dossiers eingereicht werden. Hierfür müssen bestimmte Informationsanforderungen zur Bewertung der Gefahren vorgelegt werden. Wenn jedoch keine experimentellen Daten ermittelt wurden, muss eine valide Begründung für den Datenverzicht vorgelegt werden. Für die physikalischen Gefahren wird das „waiving of testing“ vorgestellt, insbesondere wird die Vorgehensweise in IUCLID erläutert.