Flammability hazard analysis of imidazolium-based ionic liquid binary mixtures under high temperatures

Ionic liquid (IL) mixtures are promising because they can optimize the involved properties according to industrial needs. It has already been demonstrated that IL flammability is due mainly to IL decomposition generating flammable substances. Four different ILs, 1-Butylimidazolium tetrafluoroborate ([BIM][BF₄]), 1-butylimidazolium nitrate ([BIM][NO₃]), 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM][BF₄]), and 1-butyl-3-methylimidazolium nitrate ([BMIM][NO₃]), were selected as the parent salts to form the different imidazolium-based IL binary mixtures. These mixtures were tested via isothermal thermogravimetric analyzer (TGA) at different temperatures (120, 150, 180, 210, and 240 °C), then tested by the flash point analyzer after isothermal heating pretreatment at the above temperatures. Results show that the mixtures' flash point values decrease with the heating temperature increase. Vaporization of the IL mixtures’ decomposition products results in a higher concentration of flammable gases and a flash point decrease, which lead to the flammability hazard increasing. Moreover, results show that the flash points of the studied binary imidazolium IL mixtures are more similar to those of the more unstable IL in their parent ILs. Also, the flammability hazard of IL binary mixtures may obviously increase under the high temperature environment for a long time.     

Research on the critical temperature of thermal decomposition for large cartridge emulsion explosives

Emulsion explosives are one type of main industrial explosives. The emergence of the large cartridge emulsion explosives has brought new security incidents. The differential scanning calorimeter (DSC) and the accelerating rate calorimeter (ARC) were selected for the preliminary investigation of the thermal stability of emulsion explosives. The results showed that the initial thermal decomposition temperatures were in the range of 232–239 °C in nitrogen atmosphere (220–232 °C in oxygen atmosphere) in DSC measurements and 216 °C in ARC measurements. The slow cook-off experiments were carried out to investigate the critical temperature of the thermal decomposition (T_c) of the large cartridge emulsion explosives. The results indicated that the larger the diameter of the emulsion explosives, the smaller the T_c is. For the large cartridge emulsion explosives with diameter of 70 mm, the T_c was 170 °C at the heating rate of 3 °C h⁻¹. It is a dangerous temperature for the production of the large cartridge emulsion explosives and it should cause our attention.     

Case study on prevention of fire hazards in coating epoxy-based FRP work with illumination

In this study, we investigated and analyzed the causes of fire hazards on the basis of actual accidents that occurred during epoxy resin fiberglass-coating operations. Results of this study showed that during this process, two major factors could cause a fire. One factor was related to the heat produced during the mixing of the epoxy resin and a polyamide curing agent. From the results of thermal analysis, it was found that the T_onset of the epoxy resin and the polyamide curing agent was 52.8 °C by DSC and T_d10 was 58.9 °C by DT/TGA, causing an exothermic hazard. Further, the results of a pseudo-adiabatic analysis performed in a Dewar vessel showed that the temperature increased from 23.5 °C to 177 °C.The other factor that could increase fire hazard was the illumination source used during the coating operation. Depending on the type of illumination source used, the temperature could increase above 350 °C. The decomposition temperature (T_d10) of PVC was 276.3 °C. The experiments involving epoxy resin fiberglass coating using an illumination source showed serious burn marks, and the polyvinyl chloride (PVC) electrical cable emitted small flames. Therefore, it can be concluded that fire was caused by the combination of two factors—the exothermic reaction between epoxy resin and the polyamide curing agent and the effect of prolonged illumination, both of which caused an increase in temperature leading to auto-ignition of the PVC electric cable.     

Flash points measurements and prediction for binary miscible mixtures

Flash point is one of the most important parameters used to characterize the potential fire and explosion hazards for flammable liquids. In this study, flash points of twenty eight binary miscible mixtures comprised eighteen flammable pure components with different compositions were measured by using the closed cup apparatus. The obtained experimental data are further employed to develop simple and accurate models for predicting the flash points of binary miscible mixtures. Based on the vapor–liquid equilibrium theory, the normal boiling point, the standard enthalpy of vaporization, the average number of carbon atoms, and the stoichiometric concentration of the gas phase were selected as the dominant physicochemical parameters that were relevant to the overall flash point property of liquids. With these parameters for pure components as well as the compositions of mixtures, the new form of characteristic physicochemical parameters for mixtures were developed and used as the input parameters for the flash point prediction of mixtures. Both the modeling methods of multiple linear regression (MLR) and multiple nonlinear regression (MNR) were employed to model the possible quantitative relationships between the parameters for mixtures and the flash points of binary miscible mixtures. The resulted models showed satisfactory prediction ability, with the average absolute error for the external test set being 2.506 K for the MLR model and 2.537 K for the MNR model, respectively, both of which were within the range of the experimental error of FP measurements. Model validation was also performed to check the stability and predictivity of the presented models, and the results showed that both models were valid and predictive. The models were further compared to other previously published models. The results indicated the superiority of the presented models and revealed which can be effectively used to predict the FP of binary miscible mixtures, requiring only some common physicochemical parameters for the pure components other than any experimental flash point or flammability limit data as well as the use of the Le Chatelier law. This study can provide a simple, yet accurate way for engineering to predict the flash points of binary miscible mixtures as applied in the assessment of fire and explosion hazards and the development of inherently safer designs for chemical processes.     

Experimental hazardous risk investigation of energetic styphnic acid analytical reagent in calorimetric analysis

Analytical reagents identify and manage metal pollution, a major environmental issue. Regrettably, these compounds' safety concerns, especially when heated, have been neglected. This research examines the thermal hazard of the extremely reactive analytical reagent styphnic acid. Differential scanning calorimetry, thermogravimetric analysis, and accelerating rate calorimetry examined styphnic acid's thermodynamics. Thermogravimetric analysis showed weight loss reactions starting at 127 °C and peaking at 208 °C. Differential scanning calorimetry showed an endothermic peak at 176 °C. The accelerating rate calorimetry test showed that styphnic acid self-accelerates at 237 °C after 196.5 °C. Kissinger, Ozawa-Flynn-Wall, and Kissinger-Akahira-Sunose thermokinetic models calculated apparent activation energy from 131.677 to 155.718 kJ/mol. A nonlinear regression analysis showed that styphnic acid undergoes a two-step autocatalytic reaction during heat degradation. Thermal safety was assessed by measuring time to conversion limit, maximum rate, total energy release, self-accelerating decomposition temperature, and adiabatic temperature rise. Styphnic acid is less stable at higher temperatures and its thermal hazards depend on heating rate. The computed SADT was 109.04 °C, with alarm and control temperatures of 104.04 and 99.04 °C, respectively. The risk matrix analysis based on T_ad and TMR_ad suggests reducing thermal instability. This study on styphnic acid's thermal risks and safe storage and transit during analytical applications is beneficial.     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

Thermal hazard analysis of triacetone triperoxide (TATP) by DSC and GC/MS

Thermal degradation of triacetone triperoxide (TATP) was studied using differential scanning calorimetry (DSC) and gas chromatography/mass spectrometry (GC/MS). TATP, a potential explosive material, is powerful organic peroxide (OP) that can be synthesized by available chemicals, such as acetone and hydrogen peroxide in the laboratory or industries. The thermokinetic parameters, such as exothermic onset temperature (T₀) and heat of decomposition (ΔH_d), were determined by DSC tests. The gas products from thermal degradation of TATP were identified using GC/MS technique.In this study, H₂O₂ was mixed with propanone (acetone) and H₂SO₄ catalysis that produced TATP. The T₀ of TATP was determined to be 40 °C and E_a was calculated to be 65 kJ/mol. A thermal decomposition peak of H₂O₂ was analyzed by DSC and two thermal decomposition peaks of H₂O₂/propanone were determined. Therefore, H₂O₂/propanone mixture was applied to mix acid that was discovered a thermal decomposition peak (as TATP) in this study. According to risk assessment and analysis methodologies, risk assessment of TATP for the environmental and human safety issue was evaluated as 2-level of hazard probability rating (P) and 6-level of severity of consequences ratings (S). Therefore, the result of risk assessment is 12-point and was evaluated as “Undesirable” that should be enforced the effect of control method to reduce the risk.     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

Inhibiting effects of gas–particle mixtures containing CO2, Mg(OH)2 particles,and NH4H2PO4 particles on methane explosion in a 20-L closed vessel

The main risk factors from methane explosion are the associated shock waves, flames, and harmful gases. Inert gases and inhibiting powders are commonly used to prevent and mitigate the damage caused by an explosion. In this study, three inhibitors (inert gas with 8.0 vol% CO₂, 0.25 g/L Mg(OH)₂ particles, and 0.25 g/L NH₄H₂PO₄ particles) were prepared. Their inhibiting effects on methane explosions with various concentrations of methane were tested in a nearly spherical 20-L explosion vessel. Both single-component inhibitors and gas–particle mixtures can substantially suppress methane explosions with varying degrees of success. However, various inhibitors exhibited distinct reaction mechanisms for methane gas, which indicated that their inhibiting effects for methane explosion varied. To alleviate amplitude, the ranking of single-component inhibitors for both explosion pressure (P_ex) and the rate of explosion pressure rise [(dP/dt)_ex] was as follows: CO₂, NH₄H₂PO₄ particles, and Mg(OH)₂ particles. In order of decreasing amplitude, the ranking of gas‒particle mixtures for both P_ex and (dP/dt)_ex was as follows: CO₂–NH₄H₂PO₄ mixture, CO₂‒Mg(OH)₂ mixture, and pure CO₂. Overall, the optimal suppression effect was observed in the system with the CO₂–NH₄H₂PO₄ mixture, which exhibited an eminent synergistic effect on methane explosions. The amplitudes of P_ex with methane concentrations of 7.0, 9.5, and 11.0 vol% decreased by 37.1%, 42.5%, and 98.6%, respectively, when using the CO₂–NH₄H₂PO₄ mixture. In addition, an antagonistic effect was observed with CO₂‒Mg(OH)₂ mixtures because MgO, which was generated by the thermal decomposition of Mg(OH)₂, can chemically react with water vapor and CO₂ to produce basic magnesium carbonate (xMgCO₃·yMg(OH)₂·zH₂O), thereby reducing the CO₂ concentration in a reaction system. This research revealed the inhibiting effects of gas‒particle mixtures (including CO₂, Mg(OH)₂ particles, and NH₄H₂PO₄ particles) on methane explosions and provided primary experimental data.     

The thermal hazard evaluation of 1,1-di (tert-butylperoxy) cyclohexane by DSC using non-isothermal and isothermal-kinetic simulations

1,1-Di (tert-butylperoxy) cyclohexane (DTBPH) has been widely employed in the chemical industry. Unfortunately, organic peroxides have been involved in many serious fires and explosions in manufacturing processes, storage, and transportation. This study investigated the thermokinetic parameters by isothermal kinetic and non-isothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. DSC was applied to assess the kinetic parameters, such as kinetic model, frequency factor (ln k₀), activation energy (E_a), reaction order, and heat of reaction (ΔH_d). Comparisons of non-isothermal and isothermal-kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBPH. Simulations of a 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, the optimal conditions for use of DTBPH to avoid violent runaway reactions during the storage and transportation were determined. This study established the features of thermal decomposition that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.     

Experimental investigation of the complex deflagration phenomena of hybrid mixtures of activated carbon dust/hydrogen/air

This paper aims to develop quantitative insights based on measured deflagration parameters of hybrid mixtures of activated carbon (AC) dust and hydrogen (H₂) gas in air. The generated experimental evidence is used to reject the claim of the null hypothesis (H₀) that severity of deflagrations of H₂/air mixtures always bound the severity of deflagrations of heterogenous combustible mixtures of AC dust/H₂/air containing the same H₂ concentrations as in the H₂/air binaries. The core insights of this investigation show that the maximum deflagration pressure rise (ΔP_MAX) and maximum rate of pressure rise ((dP/dt)_MAX) of this hybrid mixture are greater than those corresponding to deflagrations of H₂/air mixtures for all the dust and H₂ concentrations being examined. The deflagration severity indices (K_St and ES) of the hybrid mixture containing 29 mol% H₂ are found to be greater than those of the H₂/air mixture containing 29 mol% H₂. Also, the minimum explosible concentration (MEC) of the hybrid mixture is lower than that of the AC dust in air only. The insights gained should lead to better realization of the severity of a postulated safety-significant accident scenario associated with on-board cryoadsorption H₂ storage systems for fuel-cell (FC) powered light-duty vehicles. The identified insights could also be relevant to other industrial processes where combustible dusts are generated in the vicinity of solvent vapors. Moreover, these insights should be useful for supporting quantitative risk assessment (QRA) of on-board H₂ storage systems, designing improved safety measures for cryoadsorption H₂ storage tanks, and guiding H₂ safety standards and transportation regulations.     

DDT and detonation propagation limits in an obstacle filled tube

Experiments with hydrogen–air and ethylene–air mixtures at atmospheric pressure were carried out in a 6.1 m long, 0.1 m diameter tube with different obstacle configurations and ignition types. Classical DDT experiments were performed with the first part of the tube filled with equally spaced 75 mm (44% area blockage ratio) orifice-plates. The DDT limits, defining the so-called quasi-detonation regime, where the wave propagates at a velocity above the speed of sound in the products, were found to be well correlated with d/λ = 1, where d is orifice-plate diameter and λ is the detonation cell size. The only exception was the rich ethylene limit where d/λ = 1.9 was found. In a second experiment detonation propagation limits were measured by transmitting a CJ detonation wave into an obstacle filled (same equally spaced 44% orifice plates) section of the tube. An oxy-acetylene driver promptly initiated a detonation wave at one end. In this experiment the quasi-detonation propagation limits were found to agree very well with the d/λ = 1 correlation. This indicates that the d/λ = 1 represents a propagation limit. In general, one can conclude that the classical DDT limits measured in an orifice-plate filled tube are governed by the wave propagation mechanism, independent of detonation initiation (DDT process) that can occur locally in the obstacles outside these limits. For rich mixtures, transmission of the quasi-detonation into the smooth tube resulted in CJ detonation wave. However, in a narrow range of mixtures on the lean side, the detonation failed to transmit in the smooth tube. This highlights the critical role that shock reflection plays in the propagation of quasi-detonation waves.     

Decolorization of synthetic Methyl Orange wastewater by electrocoagulation with periodic reversal of electrodes and optimization by RSM

Treatment of Methyl Orange (MO), an azo dye, synthetic wastewater by electrocoagulation with periodic reversal of the electrodes (PREC) was examined. Response Surface Methodology (RSM) was used to optimize the influence of experimental conditions for color removal (CR), energy consumption (ENC), electrode consumption (ELC) and sludge production (SP) per kg MO removed (kg(MO_r)) with optimal conditions being found to be pH 7.4, solution conductivity (к) 9.4 mS cm⁻¹, cell voltage (U) 4.4 V, current density (j) 185 mA cm⁻², electrocoagulation time (T) 14 min, cycle of periodic reversal of electrodes (t) 15 s, inter-electrode distance (d) 3.5 cm and initial MO concentration of 125 mg L⁻¹. Under these conditions, 97 ± 2% color was removed and ENC, ELC and SP were 44 ± 3 kWh kg(MO_r)⁻¹, 4.1 ± 0.2 kg(Al) kg(MO_r)⁻¹ and 17.2 ± 0.9 kg(sludge) kg(MO_r)⁻¹, respectively. With the enhanced electrochemical efficiency resulting from the periodic electrode reversal, the coefficients of increased resistance and decreased current density between the two electrodes in the PREC setup were 2.48 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.29 mA cm⁻² min⁻¹, respectively, as compared to 7.72 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.79 mA cm⁻² min⁻¹ as measured for the traditional electrocoagulation process. The rate constant of decolorization was also enhanced by 20.4% from 0.152 min⁻¹ in the traditional electrocoagulation process to 0.183 min⁻¹ in the PREC process. These performance characteristics indicate that the PREC approach may be more promising in terms of practical application, as a cost-effective treatment, than conventional electrocoagulation for textile dye removals.     

Calorimetric behaviors of N2H4 by DSC and superCRC

The objective of this study is to obtain information about the thermal decomposition behaviors of hydrazine (N₂H₄) caused by metals, using differential scanning calorimeter (DSC) and SuperCRC. The DSC measurements revealed that the exothermic reactions of N₂H₄ were caused by the reaction conditions such as the type of cells; the T_DSC with a gold pan is 485.2 K and that with a glass capillary is 620.5 K. Besides, the activation energy of the thermal decomposition of N₂H₄, calculated from the Kissinger and Ozawa methods, were found to be about 38±2 kJ mol⁻¹ in the gold pan and 141±8 kJ mol⁻¹ in the glass capillary. Moreover, a heat flow profile was observed with SuperCRC during the mixing of N₂H₄ and the metal ion solution at 298 K. The maximum heat flow was related to the metal ion oxidative characters. The higher oxidative characters would provide a faster acceleration for the exothermic behavior than the lower oxidative ions. Based on this study, Mn(VII) and Cr(VI) were considered to exhibit strongly oxidative characteristics during mixing with N₂H₄.     

Modeling of a sequencing batch reactor treating municipal wastewater using multi-layer perceptron and radial basis function artificial neural networks

A sequencing batch reactor was modeled using multi-layer perceptron and radial basis function artificial neural networks (MLPANN and RBFANN). Then, the effects of influent concentration (IC), filling time (FT), reaction time (RT), aeration intensity (AI), SRT and MLVSS concentration were examined on the effluent concentrations of TSS, TP, COD and NH₄⁺-N. The results showed that the optimal removal efficiencies would be obtained at FT of 1 h, RT of 6 h, aeration intensity of 0.88 m³/min and SRT of 30 days. In addition, COD and TSS removal efficiencies decreased and TP and NH₄⁺-N removal efficiencies did not change significantly with increases of influent concentration. The TSS, TP, COD and NH₄⁺-N removal efficiencies were 86%, 79%, 94% and 93%, respectively. The training procedures of all contaminants were highly collaborated for both RBFANN and MLPANN models. The results of training and testing data sets showed an almost perfect match between the experimental and the simulated effluent of TSS, TP, COD and NH₄⁺-N. The results indicated that with low experimental values of input data to train ANNs the MLPANN models compared to RBFANN models are more precise due to their higher coefficient of determination (R²) and lower root mean squared errors (RMSE) values.