Thermal hazard evaluation of tert-butyl hydroperoxide mixed with four acids using calorimetric approaches

Possessing thermal instability inherently, organic peroxides have caused many severe accidents in chemical industries all over the world. tert-Butyl hydroperoxide (TBHP) is usually used as initiator or oxidant because of its strong oxidizing ability in the chemical process. In this study, the thermal hazard analysis of TBHP mixed with various acids was investigated. Differential scanning calorimetry (DSC) and vent sizing package 2 were used to figure out the thermal runaway behaviors of TBHP. Thermokinetic parameters, such as exothermic onset temperature (T ₀), maximum temperature (T _max), and enthalpy (ΔH), were obtained from thermal curves. In addition, the activation energy (E _a) and rate constant (k) were calculated by the Arrhenius equation. Therefore, the T ₀ was determined to be 91.6 °C for exothermic reaction using DSC under 4 °C min^?1 of heating rate. The E _a for exothermic reaction was calculated to be 92.38 kJ mol^?1 by DSC in this study. As far as loss prevention is concerned, thermokinetic parameters are crucial to the relevant processes in the chemical industries, particularly under process upsets.     

Thermal runaway reaction evaluation of benzoyl peroxide using calorimetric approaches

Benzoyl peroxide (BPO) has been used as initiator or medicine in the chemical industries. Several thermal runaway reactions, fires, and explosions have occurred in Taiwan due to its thermal reactivity and explosive properties. A serious accident was analyzed occurring at Fu-Kao Chemical Plant in Taiwan because of runaway reaction in a batch reactor including methyl acrylate (MA), acrylic acid (AA), and BPO. This accident resulted in one death and more than 100 injuries. Differential scanning calorimetry and thermogravimetry (TG) were used to investigate and calculate the thermal hazard and safety parameter of BPO. Finally, the effects of MA and AA mixed with BPO by DSC/TG were analyzed in this study. The T ₀ of BPO was 109 °C in this study. Therefore, the T ₀ of BPO/MA was calculated to be 105 °C by DSC. AA and MA were identified as catalyst for thermal decomposition of BPO.     

Isothermal versus non-isothermal calorimetric technique to evaluate thermokinetic parameters and thermal hazard of tert-butyl peroxy-2-ethyl hexanoate

Liquid organic peroxides have been broadly employed in the process industries such as tert-butyl peroxy-2-ethyl hexanoate (TBPO). This study investigated the thermokinetic parameters of TBPO, a typical liquid organic peroxide, by isothermal kinetic algorithms and non-isothermal kinetic algorithms with thermal activity monitor III, and differential scanning calorimetry, respectively. An attempt has been made to determine the thermokinetic parameters by simulation software, such as exothermic onset temperature (T ₀), maximum temperature (T _max), decomposition (?H _d), activation energy (E _a), self-accelerating decomposition temperature, and isothermal time to maximum rate (TMR_iso). A liquid thermal explosion model was established for a reactor containing liquid organic peroxide of interest. From experimental results, liquid organic peroxides?? optimal conditions for avoiding a violent runaway reaction of storage and transportation were created.     

Thermal hazard analyses of organic peroxides and inorganic peroxides by calorimetric approaches

Organic peroxides (OPs) and inorganic peroxides (IPs) are usually employed as an initiator for polymerization, a source of free radicals, a hardener, and a linking agent in low density polyethylene (LDPE), polyvinyl chloride (PVC), controlled-rheology polypropylene (CR-PP), and styrene industries. Worldwide, due to their unstably reactive natures, OPs and IPs have caused many serious thermal explosions and runaway reaction incidents. This study was conducted to elucidate its essentially hazardous characteristics. To analyze the runaway behavior of OPs and IPs in the traditional process, thermokinetic parameters including heat of decomposition (??H _d ), exothermic onset temperature (T ₀), self-accelerating decomposition temperature (SADT), time to maximum rate (TMR), critical temperature (T _c ), etc., were measured by calorimetric approaches involving differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and calculation method. Safety and health handling information of hazardous materials and toxic substances is noted in material safety data sheets (MSDS) and was applied to analyze in process safety management (PSM) in the chemical industries, but MSDS are not providing important handling indicators concerning the SADT, TMR, T _c , etc. In view of loss prevention, more useful indicators must be provided in the sheets or guide book.     

Thermal hazard evaluation of lauroyl peroxide mixed with nitric acid

Many thermal runaway incidents have been caused by organic peroxides due to the peroxy group, -O-O-, which is essentially unstable and active. Lauroyl peroxide (LPO) is also sensitive to thermal sources and is incompatible with many materials, such as acids, bases, metals, and ions. From the thermal decomposition reaction of various concentrations of nitric acid (HNO3) (from lower to higher concentrations) with LPO, experimental data were obtained as to its exothermic onset temperature (T0), heat of decomposition (ΔHd), isothermal time to maximum rate (TMRiso), and other safety parameters exclusively for loss prevention of runaway reactions and thermal explosions. As a novel finding, LPO mixed with HNO3 can produce the detonation product of 1-nitrododecane. We used differential scanning calorimetry (DSC), thermal activity monitor III (TAM III), and gas chromatography/mass spectrometer (GC/MS) analyses of the reactivity for LPO and itself mixed with HNO3 to corroborate the decomposition reactions and reaction mechanisms in these investigations.     

Thermal risk evaluation of organic peroxide by automatic pressure tracking adiabatic calorimeter

An automatic pressure tracking adiabatic calorimeter (APTAC) has been developed to obtain the thermokinetic and vapor pressure data during runaway reactions. The heat onset temperature is important data for estimating the thermal hazardous materials. DTBP(di-tert-butyl peroxide)/toluene was chosen for evaluating the measurement values and the thermokinetic parameters. The relationships between the sample mass and the heat onset temperature in the addition to the maximum temperature were investigated to explain the heat of reaction measured by the APTAC. The apparatus properties and the reliability of the data obtained by the APTAC were examined on the basis of the experimental data.     

Thermal hazard analyses and incompatible reaction evaluation of hydrogen peroxide by DSC

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions worldwide. Its thermal hazards may also be incurred by an incompatible reaction with other chemical materials, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to thermal accidents by incompatibility and to discuss what might be formed by the upset situations. In this study, the thermal hazard analyses were conducted with various solvents, propanone (CH₃COCH₃), Fe₂O₃, FeSO₄, H₂SO₄, HCl, HNO₃, H₃PO₄, NaOH, LiOH, and KOH which were deliberately selected to individually mix with H₂O₂ for investigating the degree of hazard. Differential scanning calorimetry (DSC) was employed to evaluate the thermal hazard of H₂O₂-mixed ten chemicals. The results indicated that H₂O₂ is highly hazardous while separately mixed with ten materials, as a potential contaminant. Fire and explosion hazards could be successfully reduced if the safety-related data are suitably imbedded into manufacturing processes.     

Thermal hazard evaluation for methyl ethyl ketone peroxide mixedwith inorganic acids

Methyl ethyl ketone peroxide (MEKPO) possesses complex structures which have caused many incidents involving fires or explosions by mixing with incompatible substances, external fires, and others. In this study, reactivities or incompatibilities of MEKPO with inorganic acids (HCl, HNO₃, H₃PO₄ and H₂SO₄) were assessed by differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). Parameters obtained by the above-mentioned devices could be readily employed to discuss the runaway reaction, such as onset temperature (T ₀), heat of reaction (ΔH _d), time to maximum rate (TMR), maximum self heat rate (dT/dt)_max, adiabatic temperature rise (ΔT _ad), maximum pressure of decomposition (P _max) and so on. Mixing MEKPO with hydrochloric acid resulted in the lowest T ₀ among inorganic acids. Nitric acid not only lowered the T ₀ but also delivered the highest heat releasing rate or self heat rate (dT/dt), which was concluded to be the worst case in terms of contamination hazards during storage or transportation of MEKPO.     

Thermal explosion simulation and incompatible reaction of dicumyl peroxide by calorimetric technique

Dicumyl peroxide (DCPO) is usually employed as an initiator for polymerization, a source of free radicals, a hardener, and a linking agent. In Asia, due to its unstable reactive nature, DCPO has caused many thermal explosions and runaway reaction incidents in the manufacturing process. This study was conducted to elucidate its essentially thermal hazard characteristics. In order to analyze the runaway behavior of DCPO in a batch reactor, thermokinetic parameters, such as heat of decomposition (ΔH _d) and exothermic onset temperature (T ₀), were measured via differential scanning calorimetry (DSC). Thermal runaway phenomena were then thoroughly investigated by DSC. The thermokinetics of DCPO mixed with acids or bases were determined by DSC, and the experimental data were compared with kinetics-based curve fitting of thermal safety software (TSS). Solid thermal explosion (STE) and liquid thermal explosion (LTE) simulations of TSS were applied to determine the fundamental thermal explosion behavior in large tanks or drums. Results from curve fitting indicated that all of the acids or bases could induce exothermic reactions at even an earlier stage of the experiments. In order to diminish the extent of hazard, hazard information must be provided to the manufacturing process. Thermal hazard of DCPO mixed with nitric acid (HNO₃) was more dangerous than with other acids including sulfuric acid (H₂SO₄), phosphoric acid (H₃PO₄), and hydrochloric acid (HCl). By DSC, T ₀, heat of decomposition (ΔH _d), and activation energy (E _a) of DCPO mixed with HNO₃ were calculated to be 70 °C, 911 J g⁻¹, and 33 kJ mol⁻¹, respectively.     

Thermal hazard evaluations of 18650 lithium-ion batteries by an adiabatic calorimeter

In this study, the thermal hazard features of various lithium-ion batteries, such as LiCoO₂ and LiFePO₄, were assessed properly by calorimetric techniques. Vent sizing package 2 (VSP2), an adiabatic calorimeter, was used to measure the thermal hazards and runaway characteristics of the 18650 lithium-ion batteries under an adiabatic condition. The thermal behaviors of the lithium-ion batteries were obtained at normal and abnormal conditions in this study. The critical parameters for thermal hazardous behavior of lithium-ion batteries were obtained including the exothermic onset temperature (T ₀), heat of decomposition (ΔH), maximum temperature (T _max), maximum pressure (P _max), self-heating rate (dT/dt), and pressure rise rate (dP/dt). Therefore, the result indicates the thermal runaway situation of the lithium-ion battery with different materials and voltages in view the of TNT-equivalent method by VSP2. The hazard gets greater with higher voltage. Without the consideration of other anti-pressure measurements, different voltages involving 3.3, 3.6, 3.7, and 4.2 V are evaluated to 0.11, 0.23, 0.88, and 1.77 g of TNT. Further estimation of thermal runaway reaction and decomposition reaction of lithium-ion battery can also be confirmed by VSP2. It shows that the battery of a fully charged state is more dangerous than that of a storage state. The technique results showed that VSP2 can be used to strictly evaluate thermal runaway reaction and thermal decomposition behaviors of lithium-ion batteries. The loss prevention and thermal hazard assessment are very important for development of electric vehicles as well as other appliances in the future. Therefore, our results could be applied to define important safety indices of lithium-ion batteries for safety concerns.     

Thermal hazard evaluation of complex reactive substance using calorimeters and Dewar Vessel

In this paper, several small-scale screening test methods were discussed on evaluating the thermal hazard of reactive substances. Generally the sensitivities of DSC and ARC are not high enough to evaluate the thermal hazards for all reactive substance, especially, for those of complex reactions containing a phase and/or chemical reaction mechanism change in the lower temperature range. Using the C80, however, the reaction can easily be detected in the lower temperature range due to its high sensitivity. Therefore, the C80 gives generally more accurate results than DSC and ARC. Data from C80 and Dewar vessel were compared and it indicates that the Dewar vessel has also high enough sensitivity to evaluate the thermal hazard and determine the heat flux in lower temperature range of reactive substances. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal hazard studies for dicumyl peroxide by DSC and TAM

A differential scanning calorimetry (DSC) and thermal activity monitor (TAM) were used to study the thermo-kinetic parameters for dicumyl peroxide (DCPO) at various concentrations. The potential thermal hazards of intermediates and end products whose concentrations were at approximately 50, 70, 94 and 99.3 mass%, respectively, in the process of operating DCPO were investigated. Thermoanalytical curves indicate that the average heat of decomposition of various DCPO samples in a manufacturing process was 762 to 1200 J g ^-1 which made it an inherently hazardous material. In the incompatibilities study, significant thermal hazards appeared in the presence of H₂SO₄. From the TAM experiments, the synthetic process of DCPO could result in an unexpected reaction in the condition of batch addition with reactants and H₂SO₄.     

Thermal hazard analysis of inorganic peroxide initiators with varying water concentrations

Journal of Thermal Analysis and Calorimetry - Inorganic peroxide (IP) initiators are widely used as initiators in polymerization reactions. However, if IP initiators are in contact with water due...     

Losses evaluation in converters using the calorimetric technique

In this paper, a measurement technique of losses in the switching cell, based on calorimetric technique is presented. A special calorimeter was designed to be able to access the heat generated by an operating converter. Power component losses are studied according to the cyclic ratio and to operating frequency and an extraction method of the different terms of these losses, using calorimetric measurements, is presented. An accurate expression of the switching losses in the power semiconductors devices is proposed.     

Thermal hazard evaluation procedure for detoxifying system of hazardous gases by using of reaction calorimeter

The thermal behaviors of hazardous gas adsorbents were observed using a C80 calorimeter in order to develop a comprehensive thermal hazard evaluation procedure for a hazardous gas detoxifying system. Newly modified cells for the C80 were used to simultaneously monitor the pressure and the heat flow. The cells were also available for adsorbed gas switching. Adsorption/desorption experiments showed various thermal behaviors of the different gas-adsorbent combinations. The accidental incorporation of air into the cartridges proved to be a potential risk for heat generation. In addition, two kinds of experimental results in different states, static pressure and gas-circulation, were compared. As a result, the experimental apparatus used in this study exhibited the capability of evaluating the thermal hazards under the situation of accidental contamination by either air or other undesirable gases as well as normal adsorption.     

Thermal hazard analysis of cumene hydroperoxide using calorimetry and spectroscopy

Organic peroxides have been widely used in industries and are known to be self-reactive chemicals. In this paper, thermal and infrared spectroscopic analyses were carried out to obtain a better understanding of the thermally hazardous behavior of cumene hydroperoxide (CHP) with cumene solvent. The temperature and heat flow profiles of different concentrations of CHP at scanning and isothermal conditions were measured with a small scale reaction calorimeter. Furthermore, probe type in situ infrared spectroscopic measurements were performed and the reaction mechanism will be discussed in regards to both energy release and product identification.     

Thermal analysis and hazards evaluation for HTP-65W through calorimetric technologies and simulation

Journal of Thermal Analysis and Calorimetry - Di-tert-butyl peroxy-hexahydro terephthalate (HTP-65W), a newly developed organic peroxide, has been used in manufacturing...