2.2 Prozesssimulation
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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.
Final report of research activities at BAM concerning large scale fireballs of organic peroxides (OP). New models for OP fireball diameter, duration, height and Surface Emmissive Power (SEP) are proposed and discussed based on a large number of large-scale and small-scale experiments using Di-tert-butylperoxide (DTBP) as a liquid OP and heptane as a liquid hydrocarbon fuel. Finally, CFD simulations are used to predict the fireball parameters: diameter, duration, height and SEP. Also the impact on the German storage regulations for organic peroxides are discussed.
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.
Self-Accelerating Decomposition Temperature (SADT) is a safety characteristic for the transport of self-reactive substances and organic peroxides. Its determination is time-consuming and in dependence on the test method also material-consuming. As shown previously, DSC measurements, which can be carried out fast and with a few milligram of material, supply a good correlation with SADT for technical pure, liquid organic peroxides. The approach is now applied for solid organic peroxides. Besides, the parameters, which are involved in the correlation, are discussed and their effect on the result is weighted qualitatively. In addition it was shown, that the method is inapplicable in an easy manner for diluted organic peroxides and pure self-reactive substances.
Differential Scanning Calorimetry (DSC) may be used to avoid testing for explosive and self-reactive properties according to the legal regulations of chemicals substances and dangerous goods.
Demonstrated measured exothermic decomposition energy value significantly affected by numerous factors - choice of sample vessel, sample mass, baseline shape, peak shape, heating rate.