A posteriori hazard analysis and feedback information of an accidental event in the grains storage of an agrochemical product

The present study concerns a hazardous event which occurred in an industrial storage tank of a ground insecticide. A preliminary post-accident approach of the hazard evaluation is performed. The rapid report of the presence of an unstable functional group in the active product and of its potential thermal instability (CHETAH indices) has led to complete this examination by an experimental study of thermal analysis using isotherm exposition measurement (DTA) or with temperature programming by differential scanning calorimetry (DSC) and oxidability tests (BAM). The apparent kinetics of decomposition of the active matter of the ground insecticide has been represented by a global Arrhenius law.

A model designed for the simulation of heterogeneous thermal runaways based on the numerical solution of the transient mass and energy balances has been further applied to define the critical conditions of the storage and simulate its behavior.

The results obtained during this analysis with the experienced feedback allowed us on one side to explain the hazardous event and especially on the other side to modify the operating protocol of the conditions of formulation of the active matter on the inert mineral support.     

Probe into effect of the initiator on the thermal runaway hazards of methyl methacrylate bulk polymerization

The bulk polymerization of methyl methacrylate (MMA) is of great importance in chemical industry, but the polymerization process is highly hazardous, and few reports have focused on the effect of initiators on its thermal hazards. In this work, to thoroughly explore the thermal hazard characteristics, the runaway behavior of MMA bulk polymerization is investigated by a combination of thermodynamics experimental and kinetics theoretical methods. The results indicate that the presence of initiator exhibits an undesirable thermal hazard to the MMA bulk polymerization, and its exothermic behavior is also greatly influenced by the type and concentration of initiator. For azobisisoheptanenitrile (ABVN), azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) initiators as examples, the AIBN-initiated reaction has the shortest adiabatic induction period (39.51 min), whereas the BPO-initiated polymerization exhibits the strongest maximum temperature-rising rate and maximum pressure-rising rate. Under adiabatic runaway, the temperature and pressure change significantly with increasing AIBN concentration, revealing a great potential risk of thermal runaway. Kinetic parameters are calculated to further understand the thermal runaway mechanisms, showing a strong agreement with the adiabatic experimental data. Finally, based on the cooling failure scenario, severity grading is determined by the evaluation criteria. The current work provides extensive data as a reference and guidance for the process design and optimization of MMA bulk polymerization from the perspective of safety.     

Effects of environmental temperature on the thermal runaway of lithium-ion batteries during charging process

Lithium-ion batteries with relatively narrow operating temperature range have provoked concerns regarding the safety of LIBs. In this work, a series of experiments were conducted to explore the thermal runaway (TR) behaviors of charging batteries in a high/low temperature test chamber. The effects of charging rates (0.5 C, 1 C, 2 C, and 3 C), and ambient temperature (2 °C, 32 °C and 56 °C) are comprehensively investigated.The results indicate that the cell exhibited greater thermal hazard at the high charging rate and ambient temperature conditions. As the charging rate increased from 0.5 C to 3 C, more lithium intercalated in the anode prompt the TR triggered in advance, the TR onset temperature decreased from 297.5 °C to 264.7 °C. In addition, the charging time decreased with the elevated ambient temperature, resulting in a relatively higher TR onset temperature and lower maximum temperature, and the average TR critical time declined by 115–143 s. Finally, the TR required less heat accumulation with increasing of charging rate and ambient temperature, and the heat generation of side reaction played a substantial role that accounted for approximately 54%∼63%. These results provide an insight into the charging cell thermal runaway behaviors in complex operation environments and deliver valuable guidance for improving the safety of cell operation.     

An incident investigation on an unexpected loss of containment and damage to PHI-TEC II during acrylonitrile runaway tests

This article investigates a laboratory incident that occurred during the analysis of a thermal runaway reaction of acrylonitrile monomer. This failure, which was attributed to an human error, resulted in financial losses and corresponding unexpected results. The incident not only damaged the interior of the vessel and other instrument parts, but also exposed the researchers to considerable danger, necessitating their escape from the laboratory. The failure characteristics are discussed, and countermeasures are developed to prevent such a type of incident from reoccurring.     

Triboelectric charging behavior of wood particles during pellet handling processes

Electrostatic charges accumulated on wood particles through triboelectrification during their transportation and handling processes can cause hazardous electrical discharge which may further trigger dust explosion. In this work, tribo-charging behavior of different kinds of wood particles was investigated by a vibrating plate charging method. It was found that reduction in the work function difference between contact bodies might contribute to the reduction of tribo-charge generation, while the reduction of electrical resistivity of wood pellets could effectively accelerate the charge dissipation. As the particle size decreases, accumulated charges increase significantly. In contrast, higher moisture content of wood particles leads to lower charge accumulation due to an accelerated charge dissipation rate. Tribo-charging behaviors of white pellets, torrefied pellet, steam treated pellets and dark pellets have also been investigated. Compared to the white pellets, they all have shown a reduction on charge accumulation to some extent. However, results suggested that all of them have nearly equivalent tribo-charge density as coal and wheat grains used as references in this study.     

Cause analysis of the fire and explosion during crude oil desulfurization in China

A serious fire and explosion accident that resulted in massive crude oil leakage and severe environmental pollution occurred on 16 July, 2010, in Dalian Port, China. To investigate the root cause of accident and conduct a wide-range investigation, desulfurizing agent JH02, which has a similar ingredient to the desulfurizing agent HD used in Dalian Port, and TS02 were employed in this study to determine the role of desulfurizing agents in the accident. The thermal behavior of crude oil, desulfurizing agents, and their mixtures was measured by using a C80 calorimeter. By using the calorimetric data, the kinetic parameters of the chemical reaction, such as activation energy, pre-exponential factor, and self-accelerating decomposition temperature of crude oil, as well as JH02, TS02, and their mixtures, were calculated and compared. The results indicated that the direct cause of the accident was the thermal runaway initiated by the increasing instability of the crude oil–desulfurizing agent mixture. Excess pressure in the oil pipeline triggered the physical explosion, but it alone was not enough to cause a serious damage. Furthermore, a stable desulfurizing agent such as TS02 could not ensure a safe desulfurizing process. The results of this study would benefit the safety management of desulfurizing processes during production and storage.     

The influence of oxygen concentration on the composition of gaseous products occurring during the self-heating of coal and wood sawdust

This article deals with an assessment of the influence of oxygen concentration on the composition and amount of combustion products generated in the course of heating coal particles and wood sawdust at 150 °C. This was done both with normal air and at 15% oxygen in the air in an isothermal furnace. The generated gases were analyzed by a Fourier Transform infrared spectrometer. Results show that under both conditions, the same substances are formed: water, carbon dioxide, carbon monoxide and aliphatic hydrocarbons. However, the quantities changed. At 21% oxygen, the concentrations of carbon monoxide and methane were higher than at 15% oxygen both in coal and wood. The oxygen concentration was also found to affect the rates of release of CO and CO₂. The rate of release of CO was higher at 21% oxygen, but that of CO₂ was higher at 15%, indicating two different mechanisms. In all cases, the concentrations of these gases were higher for coal than for wood. The results have implications for the specification of safe conditions of storage of coal and wood substances and the selection of safety measures.