Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

Green thermal analysis for predicting thermal hazard of storage and transportation safety for tert-butyl peroxybenzoate

Liquid organic peroxides, such as tert-butyl peroxybenzoate (TBPB), have been widely employed in the petrifaction industry as a polymerization formation agent. This study investigated the thermokinetic parameters of TBPB by isothermal kinetic algorithms and non-isothermal kinetic equations, using thermal activity monitor III (TAM III) and differential scanning calorimetry (DSC), respectively. Simulations of 0.5 L, 25 kg, 55 gallon, and 400 kg reactors in liquid thermal explosion models were performed and compared to the results in the literature. A green thermal analysis was developed for a reactor containing TBPB to prevent pollution and reduce the energy consumption by thermal decomposition. It is based on the thermal hazard properties, such as the heat of decomposition (ΔH_d), activation energy (E_a), self-accelerating decomposition temperature (SADT), control temperature (CT), emergency temperature (ET), and critical temperature (TCR). From the experimental results, the optimal conditions to avoid violent runaway reactions during the storage and transportation of TBPB were determined.     

Thermal runaway reaction for highly exothermic material in safe storage temperature

Highly exothermic materials have caused many serious accidents involving storage and transportation, due to being thermally reactive. The safe storage and management of these materials is still a critical problem in many countries. Our aim was to study the thermal hazard of thermal reactive materials, such as a propellant, by employing differential scanning calorimetry (DSC) non-isothermal tests and isothermal tests, and then comparing the kinetic parameters by isothermal and non-isothermal of kinetics. The chosen approach was to obtain reliable thermal decomposition by a safe and effective method, which acquired the kinetic and safety parameters of storage conditions that could be applied as highly exothermic materials' reduction of loss prevention and energy potential for safer design during storage transport and processing operations.     

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.     

Effects of metal ions on thermal hazard of tert-butyl peroxy-3,5,5-trimethylhexanoate

As a commonly used initiator for polyethylene, tert-butyl peroxide 3,5,5-trimethylhexanoate (TBPTMH), with the molecular formula of C₁₃H₂₆O₃, is more likely to decompose and cause fires and explosions. Understanding the thermal risks of TBPTMH mixed with common metal ions, potentially in containers and pipes, is important. In this work, by using differential scanning calorimetry (DSC) and Phi-Tec adiabatic calorimetry, the effects of CuCl₂, FeCl₃, CuBr_2, and FeBr₃ on the thermal decomposition of TBPTMH were investigated. Adiabatic kinetic analysis was performed and the apparent activation energy (E_a) was calculated by thermodynamic analysis. Time to maximum rise under adiabatic conditions (TMR_ad) and the self-accelerating decomposition temperature (SADT) under different packing qualities were reckoned. It was found that the thermal risk of TBPTMH was increased while mixing these metal ions, especially CuBr₂. To ensure the safety of the substance in process industry, the temperature of TBPTMH in the presence of metal should be governed below 39.48 °C. This work was expected to provide some guidance for improving the process safety of TBPTMH.     

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.     

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.     

Comparisons of TGA and DSC approaches to evaluate nitrocellulose thermal degradation energy and stabilizer efficiencies

This study investigated the thermal degradation energy (activation energy, E_a) for nitrocellulose (NC) with low nitrogen content of 11.71 mass%, so-called NC3, by using two different kinds of thermal analysis instruments: thermogravimetric analyzer (TGA) and differential scanning calorimetry (DSC). A comparison of E_a for various nitrogen content NC samples at two scanning rates (5 and 10 °C min^?1) tested by TGA and DSC is also discussed in this paper. Meanwhile, our aim was to analyze the anti-degradation of E_a for NC with high nitrogen content, as so-called NC1. Thermal stability for NC1 with diphenylamine (DPA) was tested via DSC with 10 DPA concentrations in weights of 0, 0.25, 0.50, 0.75, 1.0, 1.25, 1.50, 1.75, 2.0, and 3.0 mass%. Experimental results indicated that E_a of NC3s was 319.91 kJ mol^?1. Moreover, that while dosing DPA into NC1 the best recipe could be employed to avoid any violent NC1 runaway and also can be used to distinguish the differences of thermal decomposition E_a between NC with different nitrogen contents. This study established a fast and efficient procedure for thermal decomposition properties of NC, and could be applied as an intrinsically safer design during relevant operations.     

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.     

Thermal hazard evaluation for iso-octanol nitration with mixed acid

2-Ethylhexyl nitrate (2-EHN), an important additive to diesel fuel, is produced from the nitration of iso-octanol with HNO₃–H₂SO₄ mixed acid. In this study, the differential scanning calorimeter (DSC), accelerating rate calorimeter (ARC) and reaction calorimeter were used to analyze the thermal stability of 2-EHN and the thermal hazard of iso-octanol nitration. Four samples with different ratios of 2-EHN to mixed acid were tested using DSC. The results indicated that more mixed acid could catalyze the decomposition of 2-EHN. Three samples were tested using ARC and the results showed that sample 4 contained the lowest onset temperatures, T_D8 and T_D24. This shows that there is a higher probability of triggering the decomposition of the product 2-EHN from the iso-octanol nitration process. This conclusion was verified using RC1e tests at different temperatures. The RC1e experiments also indicated that the overall heat generation of these reactions was considerably large despite the high yields of the nitration process at 45 °C and 55 °C. This heat generation makes these semi-batch processes difficult to control, especially on a pilot or plant scale. Based on the maximum temperature of the synthesis reaction (MTSR) corrected by the yield, the only acceptable semi-batch process is the nitration reaction at 10 °C.     

Thermal kinetics analysis of polymerization reaction of styrene-ethylbenzene system

To explore the reaction thermodynamics of a styrene-ethylbenzene mixed system, a differential scanning calorimetry (DSC) analysis was performed on the mixed system with styrene: ethylbenzene mass ratios of 1:0, 4:1, 3:2, and 2:3 at heating rates of 2.5, 5, 7.5, and 10 K/min. The activation energy of the mixed reaction system was calculated using the model-free Kissinger kinetic method, to determine a mixed system of relative stability mixing proportion. The thermodynamic parameters of the styrene-ethylbenzene mixture system at the optimal ratio were obtained using an adiabatic accelerating calorimeter. Further, dynamic thermal parameters such as the activation energy of the hybrid system, pre-exponential factor and order of reaction, TMR, TMRad, and T_D24 were calculated.     

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.     

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.     

Inhibiting effect of inhibitors on ignition sensitivity of wood dust

Wood products are easy to produce dust in the production and processing process, and have a serious explosion risk. In order to improve the safety of wood products production, the inhibiting effects of magnesium hydroxide (MTH), SiO₂, melamine polyphosphate (MPP) on the minimum ignition energy (MIE) and minimum ignition temperature (MIT) of wood dust were experimentally studied. The results showed that the inhibiting effects of inhibitors on the MIE of wood dust show the order of MPP > SiO₂>MTH. The order of the inhibiting effects on the MIT of wood dust was MPP > MTH > SiO_2. When 10% MPP was added to wood dust, the time when the flame appears (T_appear) and the time when the flame reaches the top of the glass tube (T_top) obviously rose to 80, 140 ms. Therefore, MPP had the best inhibiting effect on the ignition sensitivity of wood dust.According to thermogravimetry (TG), differential scanning calorimetry (DSC) tests, the introduction of MPP leaded to lower maximum mass loss rate (MMLR), higher temperature corresponding to mass loss of 90% (T_0.1), residual mass and heat absorption. In addition, thermogravimetric analysis/infrared spectrometry (TG-IR) results showed that MPP produced H₂O (g) and NH₃ (g) during the thermal decomposition process, which diluted the oxygen.     

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.     

Evaluation of multiple reactions in dilute benzoyl peroxide concentrations with additives using calorimetric technology

Benzoyl peroxide (BPO) is a typical organic peroxide widely used in food processing, particularly flour bleaching. Due to the unstable nature of the oxygen-oxygen bond in BPO, it readily reacts under even mid-low-temperature conditions. Lower concentrations of BPO are also potentially explosive, even when combined with acid or alkaline additives. Given the history of both potential and documented industrial accidents, this study investigates the thermal stability of various BPO concentrations when mixed with acid or alkaline solutions. In addition, differential and integral kinetic models were applied to verify that the apparent activation energy data from the differential scanning calorimetry experiments were valid. The results of autocatalysis reactions and nth-order reaction simulations presented characteristics consistent with the experimental findings. The findings in this paper can be used as a reference for BPO products that are mediated with either an acid or an alkaline solution during production, storage, transportation, or use.