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.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

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.     

Analysis of the chosen thermal and flammability parameters of dried sewage dust

The hazardous sludge disposal process in the form of landfills requires the determination inter alia of the flammable and explosion properties of dried sewage sludge dust, which has the ability to ignite and spontaneously combust when stored in silos. At a constant furnace surface temperature, the minimum ignition temperature of the sludge dust layer with a layer thickness of 5 mm is 270 °C, and for a layer thickness of 12.5 mm it is 250 °C. Two selected fire extinguishing powders for Class A, B, C and D fires were used in the study to determine the possibility of reducing the susceptibility of dried wastewater to ignition from heated surface, self-ignition and explosion parameters. The most effective extinguishing powder was ABC Favorit, which increased the value of the minimum ignition temperature of the layer (5 mm thick) to 360 °C and the spontaneous ignition temperature of the sludge with this powder increased by 22 °C at 169.6 cm³ in comparison to the sludge without extinguishing powder, respectively. The lowest self-ignition temperature of 136 °C was recorded for the largest tested volume (169.6 cm³) for dried sewage dust without any fire extinguishing powders. The biggest values of p_max and (dp/dt)_max dried sewage dust were recorded 4.8 bar and 113 bar/s respectively. By analysing the obtained test results, it can be assumed that dried sewage dust is a combustible material with properties similar to biomass.     

Explosibility and thermal decomposition behavior of nitrile rubber dust in industrial processes

The formation of nitrile rubber (NBR) dust clouds during processing can lead to a potential dust explosion under certain conditions. However, the potential explosion hazard posed by NBR dust is usually overlooked by enterprises. In this paper, the explosive properties of NBR dust are investigated using a Hartmann tube, a G-G furnace, and a 20 L explosion chamber. The results showed that NBR dust could cause explosions severe enough to be classified as St-1. In addition, the thermal decomposition behavior of NBR dust under combustion conditions was investigated using a combination of thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TGA-FTIR). The results indicated that in the early stage, NBR dust mainly undergoes self-thermal decomposition to produce a large amount of combustible gas, which combines with oxygen to form a mixed gas and cause a gas-phase explosion. In addition, the participation of oxygen could lower the initial temperature of NBR dust thermal decomposition. As a result, decomposition occurred more quickly and a large amount of combustible gas was produced, thus expanding the range of dust explosions. Furthermore, these combustible gases exhibit varying degrees of toxicity, seriously affecting the life and health safety of relevant personnel. This work provides theoretical guidance for the development of safe procedures to prevent and address problems during NBR dust processing in enterprises.     

Using thermal analysis with kinetic calculation method to assess the thermal stability of 2-cyanopropan-2-yliminourea

Azo compounds, which are commonly used as initiators and blowing agents, are also typical self-reactive materials capable of undergoing runaway reaction during storage and transportation, which can cause severe fires and accidents. To ensure the thermal safety of azo compounds in the process, transportation, and applications, this study investigated 2-cyanopropan-2-yliminourea, which can also be called V-30. First, thermal decomposition characteristics under the non-isothermal conditions were obtained using differential scanning calorimetry. Second, the collected data were combined with a mathematical model to evaluate the primary thermal hazard during the process for V-30. Then, based on a heat-transfer model, the self-accelerating decomposition temperature (SADT) was extrapolated for consideration and non-consideration of consumption of chemicals. The results showed that SADT of V-30 was less than 80 °C. Therefore, it is essential to avoid a temperature beyond SADT or the cooling system will fail. The influence of consumption was also considered for SADT in this study.     

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.     

Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

Effect of urea on detonation characteristics and thermal stability of ammonium nitrate

A study has examined the effect of urea on the thermal stability and detonation characteristics of ammonium nitrate (AN). The thermal decomposition temperature and surface morphology of samples were investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). For further research on the thermal sensitivity and shock sensitivity of the samples, the Koenen test and UN gap test were conducted. The results indicate that urea can substantially increase the thermal stability of AN (the greatest exothermic peak is increased by more than 100 °C) and reduce the thermal sensitivity of AN. However, AN-50wt. % urea mixtures can still produce a steady detonation in the UN gap test. Urea cannot reduce the ability to propagate a detonation. Possible explanations for these results are discussed.     

Calorimetry studies of ammonium nitrate – Effect of inhibitors,confinement, and heating rate

Ammonium nitrate (AN) has been widely used as a fertilizer for almost a century because it is an excellent nitrogen source. However, AN related explosions continue to occur time and again, despite the fact that AN has been extensively investigated. There have been more than 70 AN-related incidents during the last century, which reemphasize the dire need for further research on AN reactive hazards. This research focuses on the alternatives to make AN safer as a fertilizer by reducing its explosivity, by studying the effect of inhibitors, confinement, and heating rate on AN thermal decomposition using the Reactive Systems Screening Tool (RSST). First, the thermal decomposition of AN in the presence of different types of additives, including sodium bicarbonate, potassium carbonate, and ammonium sulfate, was studied under two concentrations, i.e., 2.8 wt.% and 12.5 wt.%. The results show that they are good inhibitors for AN. Second, the effect of confinement was tested by observing AN decomposition under five different initial pressures, varying from ambient pressure to 187 psig. It is concluded that confinement is dangerous to AN, which should be avoid in AN storage and transportation. Lastly, the effect of heating rate was studied by heating up AN under two heating rates of 0.25 °C min⁻¹ and 2 °C min⁻¹. The lower the heating rate, the lower the “onset” temperature detected.     

Micro calorimeter study on the thermal stability of lithium-ion battery electrolytes

With the extensive applications of lithium-ion batteries, many batteries explosion accidents were reported. The thermal stability of lithium-ion battery electrolyte could substantially affect the safety of lithium-ion battery. The C80 micro calorimeter was used to study the thermal stability of several commonly used organic solvents and electrolytes. The samples were heated in argon atmosphere and air atmosphere, respectively. The chemical reaction kinetics was supposed to fit by an Arrhenius law, then the self-accelerating decomposition temperature was calculated. It is found that most of the samples are stable in argon atmosphere while decomposing in air atmosphere, and the single organic solvent is more stable than the electrolyte generally.     

Effects of initial temperature and pressure on explosion characteristics of propane–diluent–air mixtures

The explosion characteristics of propane–diluent–air mixtures under various temperatures and pressures were investigated using a 20-L apparatus. The explosion limits of propane diluted with nitrogen or carbon dioxide were measured at high temperatures from 25 to 120 °C. The results showed that the upper explosion limit (UEL) increased, and the lower explosion limit (LEL) decreased with the rising temperature. The explosion limits of propane diluted with nitrogen or carbon dioxide were also measured at high pressures from 0.10 to 0.16 MPa. The results showed that the UEL increased, and the LEL almost remainedunchanged along with increased pressure. Under the same initial operating conditions, the concentration of nitrogen required to reach the minimum inerting concentration (MIC) point was higher than the concentration of carbon dioxide. Finally, the study investigated the limiting oxygen concentration (LOC) of propane under various initial temperatures, initial pressures, and inert gases. The LOC of propane decreased approximately linearly with increased temperature or pressure, and the LOC of propane dilution with carbon dioxide was greater than dilution with nitrogen from 25 to 120 °C or from 0.10 to 0.16 MPa, which indicated that the dilution effect of carbon dioxide was better than that of nitrogen.     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

Modelling breakdown of industrial thermal insulation during fire exposure

The aging of many of the installations in the oil and gas industry may increase the likelihood of loss of containment of flammable substances, which could lead to major accidents. Flame temperatures in a typical hydrocarbon fire may reach 1100–1200 °C, which are associated with heat flux levels between 250 and 350 kW/m². To limit or delay the escalation of an initial fire, passive fire protection (PFP) can be an effective barrier. Additionally, both equipment and piping may require thermal insulation for heat or cold conservation. Previous studies have investigated whether thermal insulation alone may protect the equipment for a required time period, e.g., until adequate depressurization is achieved. The present study entails the development of a numerical model for predicting the heat transport through a multi-layer wall of a distillation column exposed to fire. The outer surface is covered by stainless-steel weather protective cladding, followed by PFP, thermal insulation, and finally an inner column of carbon steel of variable thicknesses. The model for the breakdown of thermal insulation is based on observed dimensional changes and independent measurements of the thermal conductivity of the insulation after heat treatment. The calculated temperature profiles of thermally insulated carbon steel during fire exposure are compared to fire test results for carbon steel with thicknesses of 16, 12, 6 and 3 mm. The model's predictions agree reasonably well with the experiments. The degradation of the thermal insulation at temperatures above 1100 °C limits its applicability as fire protection, especially for low carbon-steel thickness. However, the model predicts that adding a 10-mm layer of more heat-resistant insulation (PFP) inside the fire-exposed cladding may considerably extend the time to breakdown of the thermal insulation.     

Influence of coal particles on methane/air mixture ignition in a heated environment

The temperature at which coal dust glows is normally much lower than the auto-ignition temperature (AIT) of methane/air mixtures, and thus a better understanding is needed regarding methane/air ignition in a heated environment in the presence of coal particles. A horizontal tube apparatus was used to test the effect of brown coal and two kinds of bituminous and anthracite on methane/air combustibility. For the four coal samples tested, the presence of coal particles significantly reduced the minimum temperature for ignition of methane/air mixtures in a heated environment. No. 1 bituminous coal with 12 mm diameter decreased the ignition temperature value from 595 to 500 °C. It is thought that pre-ignition of low-AIT volatiles emitted from the heated coal particles ignited the methane/air mixtures. Volatiles, sulfur content, and large porosity of piled coal particles all enhanced ignition of methane/air mixtures in a hot environment, while water content and small particle size reduced ignition. For anthracite, no ignition occurred when temperatures of the heated environment were lower than the AIT of methane (595 °C), except for the 12-mm-diameter sample. Anthracite did not readily ignite methane/air mixtures and the ignition mechanism was somewhat similar to that of a burning cigarette.     

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.     

膨胀聚苯乙烯热分解动力学分析和寿命预测

针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下的热解过程可由自催化n阶反应机理描述。阻燃EPS在空气气氛下的热解机理为自催化n阶反应,在氮气气氛下则为n阶反应机理。基于动力学参数和反应机理,对聚苯乙烯泡沫在不同温度下的寿命进行了预测。     

Sensitivity analysis and optimization for gasoline vapor condensation recovery

Volatile organic compounds (VOCs) are easily evaporated and discharged from everywhere into the atmosphere, especially in various operations of gasoline. The emission of VOCs is always a significant environmental problem, and the control of VOCs pollution has been a hot topic in the field of air purification. In this paper, the condensation separation method for gasoline vapor recovery was investigated and four gasoline vapors of S1–S4 were selected for the sensitivity analysis and optimization of the condensation process, using the Model Analysis Tools from Aspen Plus. Generally, to control VOCs pollution efficiently, both the vapor recovery efficiency and the outlet vapor concentration of the condensation recovery system should be simultaneously considered. Then an optimized three-stage condensation process was proposed, whose condensation temperatures were optimized and designed at 1 °C, −40 °C and −110 °C, respectively. Further, based on the comprehensive consideration of both meeting the more strict VOCs emission standard and ensuring the condensation recovery system work stably and economically, it was recommended that the maximum total vapor recovery efficiencies for S1–S4 should be 99.73%, 99.79%, 99.82% and 99.19%, and the minimum outlet vapor concentrations be 2.87 g/m³, 2.75 g/m³, 3.04 g/m³ and 16.98 g/m³, respectively. Accordingly, the condensation temperature of the copious cooling stage should be set at −130 °C. Moreover, the total cooling duties for the single-stage and three-stage condensation processes were investigated and compared when the condensation temperature of the recovery system ranged from 20 °C to −110 °C. The total cooling duties of the three-stage condensation process for S1–S4 would be saved by 12.23%, 15.68%, 13.96% and 15.65%, respectively. Finally, a three-stage condensation system was developed for the industrial gasoline vapor recovery, which has performed well since its installation.     

Investigation of how pressure influences the thermal decomposition behavior of azodicarbonamide

Azodicarbonamide (ADC) is a type of azo compound with outstanding application performance, it is always used as a blowing agent in the production of foamed plastics. Based on previous studies, it has been considered harmless in its practical application process. Nevertheless, our research has overturned this standpoint and denoted the special exothermic behavior of ADC under specific use processes, especially when it was placed in a high-pressure system. In this study, a simultaneous thermogravimetric analyzer (STA) was employed to preliminarily evaluate the thermal stability of ADC under atmospheric pressure. Followed with calorimetric experiments by high-pressure differential scanning calorimetry (HP DSC), the exothermic behaviors of ADC under different initial furnace pressures were investigated. The obtained results revealed that the thermal decomposition rate of ADC linearly increases along with increasing testing pressure, which shows a highly autocatalytic characteristic. The peak power of DSC curve breathtakingly reached 73 W/g when the initial testing pressure was set at 4 MPa, and the overall decomposition heat reached 1261 J/g with the scanning rate at 4 ^°C/min. Furthermore, the decomposition mechanism, thermal hazards, and explosion potential were comprehensively evaluated in this study for the first time.