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.     

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.     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

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.     

Numerical simulation of the thermal inertia of an adiabatic reaction calorimeter in reaction thermal safety process

Obtaining accurate thermal risk assessment parameters of chemical processes and substance properties is essential for improving the safety of chemical production and substance use and storage, and the adiabatic reaction calorimeter (ARC) has been employed by many researchers for this purpose. However, with the improvement and upgrading of the instrument, an examination of the factors that affect its detection accuracy is warranted. A simplified reaction model of the adiabatic thermal decomposition of tert-butyl peroxyacetate was constructed using computational fluid dynamics in which the adiabatic thermal decomposition kinetic model and fluid-solid coupling model were combined to simulate heat transfer. To verify the reliability of the parameters of the numerical calculation model, the effects of the sample cell's material, wall thickness, and mass were investigated in relation to the thermal inertia of the ARC. The results indicated that the thermal inertia of the system was lowest when the sample cell was composed of titanium. When the sample pool's composition is determined, the thermal inertia of the system can be reduced to a certain extent through an approximate increase in the sample mass. Finally, an analysis of the heat flow cloud diagram of the wall of sample pools made from different materials revealed that the thermal conductivity of titanium was high; this information can assist in controlling the adiabatic process.     

Thermal decomposition mechanism of 65% lysine sulfate powder and its thermal stability based on thermal analysis

Lysine is widely used in the fields of food, medicine and feed, which generally appears in the form of lysine sulfate or lysine hydrochloride dust because of the high instability of the free L-lysine. The L-lysine Sulfate is in high risk of decomposition, spontaneous ignition and even the dust explosion, because the control temperature in its production process is high up to 90 °C. Thus, the thermal behaviors and its thermal stability of 65% lysine sulfate are experimentally explored in Air and Nitrogen using the simultaneous TG-DSC measurements. Results show: (1) the decomposition of 65% lysine sulfate can be divided into three stages both in the atmospheres of air and nitrogen, and most of the weight loss occurred in the first two stages, which are related with the decarboxylation and deamination process. (2) The effects of atmosphere on the decomposition of 65% lysine sulfate mainly occur at the third stage. In this stage, the weight loss in nitrogen is only 14.2%, which is much lower than that in air (34.3%), which is related to the oxidative degradation at high temperature. Besides, the active energy is slightly increased in nitrogen compared to that in air. (3) The initial temperatures of the decomposition of the 65% lysine sulfate are 145 °C and 155 °C, for the air and nitrogen atmosphere, respectively, which are much lower than that (260 °C) of the pure lysine.     

Peculiar effect of acylamino and cyan groups on thermal behavior of 2-(1-cyano-1-methylethyl)azocarboxamide

2-(1-Cyano-1-methylethyl)azocarboxamide (CABN) is a representative of new-type azo initiator in the radical polymerization industry. The peculiar water and oil soluble characters make it a versatile rising star for the industry to initiate the polymerization of monomers in either polar or nonpolar solvents based continuous phases. This paper decodes the effect of acylamino and cyan groups on thermal stability and hazards of CABN via advanced thermokinetic analysis and numerical simulation. Initially, simultaneous thermogravimetric analyzer was employed to evaluate the thermal stability of CABN and its two structurally similar azo compounds (azos), azobisisobutyronitrile (AIBN) and azodicarbonamide (AC). Followed with calorimetric experiments by differential scanning calorimetry, the effect of two functional groups on thermal behavior parameters, such as decomposition temperature, melting point, and heat of decomposition was estimated. The results indicated that the acylamino group can improve the thermal stability of CABN but with bulkier heat release. Ultimately, through the medium of thermokinetic analysis, the thermal hazard of AIBN, CABN, and AC was simulated based on auto-ignition and thermal explosion theory. The research results would provide references for the synthesis of new-type azo initiators and process safety parameters to the polymerization industry.     

Ammonium nitrate thermal decomposition with additives

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na₂SO₄) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.     

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.     

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.     

Effects of typical additives on the thermal stability of ammonium peroxydisulfate

Ammonium peroxydisulfate (APS), one of the most widely used inorganic peroxides in the process industries, is a thermally unstable peroxide and potent oxidizer due to the presence of peroxy bond in the molecule and is incompatible with most substances. To investigate the effect of typical additives on the thermal decomposition of APS, in this paper, diamine phosphate (DAP), monoamine phosphate (MAP), and aluminum hydroxide (AH) were selected as additives; pure APS and samples with 10 wt% and 20 wt% of additives were first tested by differential scanning calorimetry (DSC). The experiments and analysis showed that the samples with 10 wt% of additive had better thermal stability than those with 20 wt% of additive. After screening, the three groups of 10 wt% AH, 10 wt% MAP, and 20 wt% MAP additive conditions could be considered to have a better thermal stability effect on the thermal decomposition of APS. Four groups of samples were, in turn, tested by Phi-Tec II. The adiabatic results showed two discontinuous exothermic processes; 10 wt% AH promoted the weak exothermic effect in the first stage. In contrast, the three groups of additives in the main exothermic stage showed different degrees of inhibition, and the inhibiting effect was ranked as 10 wt% AH, 10 wt% MAP, and 20 wt% MAP in order. Finally, the self-accelerated decomposition temperature (SADT) was calculated under the 25 kg standard package. The adiabatic results, including SADT, were combined to render feasible recommendations for the use of additives, which provides references for the packaging and transportation of additives and their applications.     

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.     

Research on thermal decomposition characteristics of H foaming agent with different moisture contents

N, N-Dinitroso pentamethylene tetramine, also known as H foaming agent, is a self-reactive chemical substance commonly used in the rubber industry. Decomposition, explosion and combustion may be caused by the presence of fire or high temperature. As a high-risk chemical that is strictly regulated in China, H foaming agent has ever triggered multiple accidents. During the study of the decomposition thermal process of H foaming agent, it was found that the presence of moisture content at different levels had a significant effect on its thermal stability. The thermal characteristics of H foaming agent under different moisture contents was studied through the test means such as adiabatic calorimetry and high-pressure differential scanning calorimetry. Through isothermal calorimetry experiment, it was found that the decomposition of H foaming agent had obvious auto-catalytic characteristics. In the moisture content within the range of 0–40%, with the increase of moisture content, the initial exothermic temperature T_onset of the mixture system of H foaming agent and water decreased, while the time from initial heat release to rapid temperature rise of the reaction system (induction period) was gradually prolonged, and the temperature increment of the reaction system was increased gradually. As the proportion of moisture content in the system increased, the adiabatic temperature rise ΔT_ad of the mixture system of H foaming agent and water gradually decreased, meanwhile the time to maximum rate under adiabatic condition (TMR_ad) gradually decreased. The research results have guiding significance for finding the reasonable moisture content of H foaming agent in the drying process and determining the upper temperature limit during storage and transportation.     

The application of kinetics based simulation method in thermal risk prediction of coal

Coal spontaneous combustion is one of the major natural disasters faced in coal mines. The accurate prediction of the thermal risk of coal is of great importance. However, there isn't a widely accepted approach to get the oxidation process of coal that under adiabatic condition or in a specific environment under mine at present. To demonstrate whether the advanced kinetics simulation method could be employed to obtain the accurate oxidation process of coal for determining the coal's thermal risk in the mine design phase and mining phase, DSC experiments were conducted by C80 micro-calorimeter to get the heat behavior of coal, based on which the kinetic parameters can be solved and the oxidation process of coal can be predicted.The results showed that the kinetics based simulation method was successfully used to predict the adiabatic temperature rise process of coal for risk prediction. The deviation between the predicted curve and tested curve that obtained by adiabatic test is small enough to be accepted. Kinetics based simulation method is a promising candidate, instead of adiabatic test, to assess the propensity of coal to spontaneous combustion, which can play an important role in the design phase of the mine and mining area. Moreover, through establishing the heat balance equation of residual coal and with the aid of kinetics based simulation method, the oxidation process of coal that in the suffocation zone of the gob was also accurately predicted. According to the index t₇₀ (the time required for coal to reach 70 °C) and v_min (the lower limit of the advancing speed of the working face) obtained from the predicted curve, the thermal risk of coal was predicted to guide the further adjustment of the advancing speed of the working face, the amount of the injected mud and the determination that whether to add other fire prevention measures. Kinetics based simulation method, be of great practical importance in risk prediction of coal that in the gob, can be also used as a convenient tool to guide the safe production in the actual mining process.