Explosion venting technology is widely accepted as the effective constructional protection measures against gas and dust explosions.The key problem in venting is the appropriate design of the vent area necessary for an effective release of the material i.e. the pressure developed during explosion did not cause any damage to the plant protected.Current gas explosion vent design standards in the USA (NFPA68, 2002) and European (2007) rely on the vent correlation first published by Bartknecht in 1993 (Siwek, 1996).N FPA 68 also recommends the correlation of Swift (Swift,1983)at low overpressures. For a vent to give no increase in overpressure other than that due to the pressure difference created by the mass flow of unburnt gases through the vent, the vent mass flow rate is assumed to be equal to the maximum mass burning rate of the flame and this consideration should be used as the design mass flow through the vent. Two different methods ( Method I and Method 2) have been proposed based on the Sμ and Sμ (E-1) to describe the maximum mass burning rate given as, mb = ASμpμ=CdeA(2pPμred)o.5 mb =ASgPm =AgSμ(E-I)P μ=Cde4,(2pu Pred)0,5 (2) The equation given in (2) is slightly different from (1) as is about 6.5 times the mass flow of the first method as it takes the effect of (E-1) where E is the expansion ratio. A critical review were carried out for the applicability, validity and limitation on the venting correlations adopted in NFPA 68 and European Standard with 470 literature experimental data, covering a wide range of values for vessel volume and geometries, bursting vent pressure, Pv L/D ratio, maximum reduced pressure, Pred and ignition location. The fuels involved are methane, propane, hydrogen, town gas, ethylene, acetone/air mixtures with the most hazardous near-stoichiornetric fuel-air concentration. Besides, Molkov's equation (Molkov, 2001) which is regarded as alternative venting design offered in NFPA 68 and Bradley and Mitcheson's equation for safe venting design were also analysed on the experimental data for their validity and limitation as well as the proposed methods. From the results, it is clear that Bartknecht's equation gave a satisfactory result with experimental data for K <-5 and Swift's equation (Swift, 1983) can be extended to wider range for Pred> 200 mbar, providing the parameter PV is added into the equation. Method 2 gave a good agreement to most of the experimental data as it followed assumptions applied for correlations given by Bradley and Mitcheson for safe venting design (Bradley and Mitcheson, 1978a,B radley and Mitcheson, 1978b). It is also proven that the vent coefficient, K is confident to be used in quantifying the vessel's geometry for cubic vessel and the use of As/Av term is more favourable for non-cubic vessels. To justify the validity and applicability of the proposed methods, series of simply vented experiments were carried out, involving two different cylindrical volumes i.e. 0.2 and 0.0065 M3. It is found that self acceleration plays important role in bigger vessel in determining the final Pmax inside the vessel. Method 2 gave closer prediction on Pmax in respect with other studied correlations. The investigation of vented gas explosion is explored further with the relief pipe been connected to the vessel at different fuel/air equivalence ratios, ignition position and Pv. The results demonstrate that the magnitude of Pmax was increased corresponding to the increase of Pv- From the experiments,it is found that peak pressure with strong acoustic behaviour is observed related to increase in Pv and in some cases,significant detonation spike was also observed particularly in high burning velocity mixtures. It is found that substantial amount of unburnt gases left inside the vessel after the vent burst is the leading factor in increase of Pmax for high burning velocity mixtures at centrally ignited. The associate gas velocities ahead of the flame create high unburnt gas flows conditions at entry to the vent and this give rise to high back pressures which lead to the severity in final Pmax inside the vessel. It was observed that end ignition leads to a higher explosion severity than central ignition in most cases, implying that central ignition is not a worst-case scenario in gas vented explosions as reported previously.

Hexahydro-1,3,5-trinitro-1,3,5-triazene (RDX) is a military explosive that has become a recalcitrant environmental pollutant over the last few decades owing to its production, storage and use. CYP177A1 (XplA) is a biotechnologically interesting and novel class of P450-flavodoxin fusion enzyme identified from Rhodococcus rhodochrous strain 11Y that catalyses the breakdown of RDX. Its redox partner is a NAD(P)H-dependent FAD-binding flavodoxin reductase (XplB). This study reports the biochemical, biophysical and structural properties of these two enzymes which form a novel P450 redox system with unique domain organisation. These reveal novel features for a P450 enzyme with non-standard UV/Visible spectroscopic features and unusual ligand binding properties. Unexpectedly, XplA’s affinity for imidazole is exceptionally high (Kd = 1.57 μM), explaining previous reports of a red- shifted XplA Soret band in pure enzyme. XplA’s true Soret maximum is at 417 nm. Similarly, the XplA flavodoxin domain displays unusually weak FMN binding (Kd = 1.09 μM), necessitating its reconstitution with the FMN cofactor. Ligand binding data demonstrate XplA’s constricted active site, which can only accommodate RDX and small inhibitory ligands (e.g. 4-phenylimidazole and morpholine) while discriminating against larger azole drugs. The crystal structure identifies a high affinity imidazole binding site, consistent with its low Kd, and shows active site penetration by PEG, perhaps indicative of an evolutionary lipid metabolising function for XplA. The substrate-free heme iron potential (-268 mV vs. NHE) is positive for a low spin P450, consistent with the predominantly reductive role of XplA. The elevated potential of the FMN semiquinone/hydroquinone couple (-172 mV) is also consistent with this functional adaptation. The XplB reductase partner could not be isolated with the FAD cofactor incorporated to make holoprotein. However, the protein was isolated in a soluble and homogenous state which demonstrated very weak FAD affinity. XplB’s ability to interact with XplA and a pyridine nucleotide coenzyme was demonstrated, indicating the enzyme was functional in the presence of FAD. XplA’s unusual molecular selectivity, structural and thermodynamic properties likely reflect its evolution as a specialised RDX reductase catalyst.

La maîtrise des risques d'incendie et d'explosion dans les procédés industriels repose sur une évaluation des conditions d'occurrence et des conséquences prévisibles de ces évènements. L'étude du retour d'expérience relatif aux accidents industriels impliquant des produits combustibles met souvent en évidence la méconnaissance des dangers des produits par les opérateurs et/ou une évaluation insuffisante ou incomplète des risques générés par le procédé exploité. Les évolutions réglementaires intervenues ces dix dernières années ont pour objectif de mieux identifier et gérer ces risques. Pour autant, afin de réduire la fréquence et la gravité de ces accidents, il est nécessaire d'améliorer encore la sécurité des procédés qui mettent en oeuvre des produits combustibles. C'est lorsque cette évaluation est la plus juste et réaliste que les mesures de prévention et de protection sont adaptées. Ceci nécessite avant tout de caractériser les dangers présentés par les produits stockés, transportés ou utilisés. Il est ensuite nécessaire de mieux identifier et gérer les risques induits. Les travaux effectués ont été consacrés en premier lieu à la caractérisation réglementaire des dangers physico-chimiques des substances et des mélanges, ainsi qu'à l'évaluation de l'aptitude des produits inflammables sous forme de gaz, de vapeur ou de poussière à générer des atmosphères explosives et à être enflammés. En second lieu, ces travaux se sont attachés à mettre en évidence les éléments essentiels du contexte réglementaire, normatif et méthodologique sur les thèmes des atmosphères explosives et de l'évaluation des risques associés et à développer une méthode d'étude du risque associé à la formation d'atmosphères explosives dans les installations industrielles compatible avec les exigences réglementaires applicables / Controlling fire and explosion hazards in industrial processes is based on occurrence conditions and the assessment of possible effects and consequences of these events. The feedback from industrial accidents involving combustible products often reveals an insufficient identification of products hazards and/or an incorrect or incomplete risk assessment of the processes by the operators. The regulatory evolutions in the past decade were aimed at better identification and management of these risks. Nevertheless, in order to reduce the frequency and the severity of these accidents, it is necessary to further improve the safety procedures concerning combustible materials. When this evaluation is the most accurate and realistic, prevention and protection measures are the most adequate. This requires an accurate hazard characterization of the products stored, transported or used. It is also necessary to better identify and manage the risks associated. This work has been devoted primarily to the regulatory characterization of physical and chemical hazards of substances and mixtures, as well as evaluating the ability of flammable gas, vapour or dust to form explosive atmospheres and an eventual ignition. Secondly, this work have attempted to highlight the key elements of the regulatory, normative and methodological context concerning explosive atmospheres and to develop a specific methodology allowing explosive atmospheres explosion risk assessment in industrial facilities, consistent with applicable regulatory requirements