Modeling of n-butane ignition, combustion, and preflame oxidation in the 20-l vessel

The objective of the study reported herein is to simulate various physical and chemical phenomena accompanying fuel-rich n-butane–oxygen mixture preparation, ignition, preflame oxidation, and combustion in the standard 20-l explosion vessel, by applying mathematical models. Based on the computational fluid dynamics (CFD) simulations of the mixing process and natural convection of the ignition kernel, as well as on the analysis of the detailed reaction mechanism of n-butane oxidation, laminar flame propagation, and self-ignition, possible explanations for the phenomena observed experimentally have been suggested. The results of the study indicate that seemingly inflammable mixtures can become hazardous depending on the mixture preparation procedure and forced ignition timing.     

Detailed and reduced chemistry for hydrogen autoignition

Reaction-rate parameters are given for the detailed chemistry of gas-phase hydrogen combustion, involving 21 reversible elementary steps. It is indicated that, when attention is restricted to specific combustion processes and particular conditions of interest, fewer elementary steps are needed. In particular, for calculating autoignition times over a wide range of pressures for temperatures between about 1000 and 2000 K, five irreversible elementary steps suffice, yielding a remarkable reduction in complexity. It is explained that, from a mathematical viewpoint, in terms of global reaction-kinetic mechanisms, the hydrogen–oxygen system in principle comprises only six overall steps. Rational reduced chemical mechanisms for hydrogen combustion therefore necessarily must have fewer than six overall steps. For autoignition over the range of conditions specified above, ignition times can be determined accurately by considering, in addition to an elementary initiation step and an elementary termination step, at most three overall steps for reaction intermediaries, which reduce to two for very fuel-lean conditions and to one for stoichiometric or fuel-rich conditions. The resulting reductions can simplify computations that need to be performed in risk analyses for hydrogen storage and utilization.     

On the understanding and control of the spontaneous heating of dried tannery wastewater sludge

We studied the spontaneous heating of dried sludge produced by treating wastewater mainly originating from tanneries. Heating up to burning has been observed in the presence of air and moisture, starting at ambient temperature. To understand and prevent the process we combined chemical and morphological analyses (ESEM) with thermal activity monitoring in insulated vessels. Selective additions of chemicals, either to amplify or depress the reactivity, have been used to investigate and identify both the chemical mechanism causing the sludge self-heating, and a prevention or a mitigation strategy. FeS additions accelerate the onset of reactivity, while S sustains it over time. On the contrary, Ca(OH)₂, Na₂CO₃, NaHCO₃, FeCl₂, EDTA, NaClO can limit, up to completely preventing, the exothermic activity. All the experimental evidences show that the reactions supporting the dried sludge self-heating involve the Fe/S/O system. The total suppression of the reactivity requires amounts of additives that are industrially incompatible with waste reduction and economics. The best prevention requires reduction or removal of S and Fe from the dried solid matrix.     

Low temperature autoignition of Jet A and surrogate jet fuel

An experimental study of the low-temperature and low-pressure autoignition of Jet A and surrogate fuels was conducted using the ASTM-E659 standardized test method. Two surrogate fuels (Aachen and JI mixtures), their individual components and two batches (POSF-4658 and POSF-10325) of standardized Jet A were tested using the ASTM-E659 method for a range of fuel concentrations and temperatures. The ignition behaviors were categorized into four distinct ignition modes. The individual hydrocarbon components had a wide range of ignition behaviors and minimum autoignition temperatures (AIT) values depending on the molecular structure. The two Jet A batches showed similar ignition behavior with measured AITs of 229 ±3°C and 225 ±3°C respectively. Both surrogates exhibited similar ignition behavior to Jet A with comparable AITs of 219 ±3.1°C (Aachen) and 228 ±3°C (JI) with the JI mixture proving to be a more suitable surrogate to Jet A in the low-temperature thermal ignition regime.     

Reconsidering autoignition in the context of modern process safety: Literature review and experimental analysis

Autoignition is regarded as the spontaneous combustion of a fuel without an apparent ignition source. With respect to fires and explosions in the process industries, the autoignition hazard is one that requires management and consideration. Despite the importance of understanding the autoignition hazard, the literature on the topic is often disappointingly sparse and inconsistent. Experimental methods don't adequately represent real-world conditions and are complicated by experimental error, invoking the need for a reconsideration of autoignition as it pertains to process safety. This work utilized the ASTM E659 method to study potential experimental error for the purpose of improving the process safety community's understanding of autoignition phenomena. Of interest to this study were effects of humidity and suspected occurrences of cool flames, two sources of error which have not been fully explained in the literature. For the fuels tested, results show that humidity has only a slight effect on overall autoignition behavior. However, this study's examination of cool flames suggests that they could be a common occurrence in this testing method. Analysis of these experiments show that cool flames can feature significant exothermic effects and are thus of concern from a perspective of risk management. In addition, this work proposes a novel criterion for a more conservative assessment of autoignition experiments, which results in less subjectivity of analysis.