Explosion evaluation and safety storage analyses of cumene hydroperoxide using various calorimeters

Plenty of thermal explosions and runaway reactions of cumene hydroperoxide (CHP) were described from 1981 to 2010 in Taiwan. Therefore, a thermal explosion accident of CHP in oxidation tower in 2010 in Taiwan was investigated because of piping breakage. In general, high concentration of CHP for thermal analysis using the calorimeter is dangerous. Therefore, a simulation method and a kinetic parameter were used to simulate thermal hazard of high concentrations of CHP only by the researcher. This study was applied to evaluate thermal hazard and to analyze storage parameters of 80 and 88 mass% CHP using three calorimeters for the oxidation tower, transportation, and 50-gallon drum. Differential scanning calorimetry (DSC) (a non-isothermal calorimeter), thermal activity monitor III (TAM III) (an isothermal calorimeter), and vent sizing package 2 (VSP2) (an adiabatic calorimeter) were employed to detect the exothermic behavior and runaway reaction model of 80 and 88 mass% CHP. Exothermic onset temperature (T ₀), heat of decomposition (ΔH _d), maximum temperature (T _max), time to maximum rate under isothermal condition (TMR_iso) (as an emergency response time), maximum pressure (P _max), maximum of self-heating rate ((dT/dt)_max), maximum of pressure rise rate ((dP/dt)_max), half-life time (t _1/2), reaction order (n), activation energy (E _a), frequency factor (A), etc., of 80 and 88 mass% CHP were applied to prevent thermal explosion and runaway reaction accident and to calculate the critical temperature (T _c). Experimental results displayed that the n of 80 and 88 mass% CHP was determined to be 0.5 and the E _a of 80 and 88 mass% CHP were evaluated to be 132 and 134 kJ mol^?1, respectively.     

Thermal hazard investigation of cumene hydroperoxide in the first oxidation tower

This article studies the thermokinetics and safety parameters of cumene hydroperoxide (CHP) manufactured in the first oxidation tower. Vent sizing package 2 (VSP2), an adiabatic calorimeter, was employed to determine reaction kinetics, the exothermic onset temperature (T ₀), reaction order (n), ignition runaway temperature (T _{C, I}), etc. The n value and activation energy (E _a) of 15?mass% CHP were calculated to be 0.5 and 120.2?kJ?mol^?1, respectively. The heat generation rate (Q _g) of 15?mass% CHP compared with hS (cooling rate)?=?6.7?J?min^?1?K^?1 of heat balance, the T _S,E and the critical extinction temperature (T _{C, E}) under 110?°C of ambient temperature (T _a) were calculated 111 and 207?°C, respectively. The Q _g of 15?mass% CHP compared with hS?=?0.3?J?min^?1?K^?1 of heat balance was applied to determine the T _{C, I} that was evaluated to be 116?°C. This article describes the best operating conditions when handling CHP, starting from the first oxidation tower.     

Thermal hazards evaluation of cumene hydroperoxide mixed with its derivatives

Over 90% of the cumene hydroperoxide (CHP) produced in the world is applied in the production of phenol and acetone. The additional applications were used as a catalyst, a curing agent, and as an initiator for polymerization. Many previous studies from open literature have verified and employed various aspects of the thermal decomposition and thermokinetics of CHP reactions. An isothermal microcalorimeter (thermal activity monitor III, TAM III), and a thermal dynamic calorimetry (differential scanning calorimetry, DSC) were used to resolve the exothermic behaviors, such as exothermic onset temperature (T ₀), heat power, heat of decomposition (ΔH _d), self-heating rate, peak temperature of reaction system, time to maximum rate (TMR), etc. Furthermore, Fourier transform infrared (FT-IR) spectrometry was used to analyze the CHP products with its derivatives at 150 °C. This study will assess and validate the thermal hazards of CHP and incompatible reactions of CHP mixed with its derivatives, such as acetonphenone (AP), and dimethylphenyl carbinol (DMPC), that are essential to process safety design.     

Thermal runaway analyses for two organic peroxides with H2O and dry fire-extinguishing chemicals by DSC and VSP2

In recent years, organic peroxides, including methyl ethyl ketone peroxide (MEKPO) and cumene hydroperoxide (CHP), have often caused thermal runaway reactions, fires, and thermal explosions worldwide. Under normal circumstances, H₂O and dry fire-extinguishing chemicals are often employed to eliminate fire situations. We evaluated the thermal runaway reaction for MEKPO and CHP mixed with H₂O and dry fire-extinguishing chemicals by differential scanning calorimetry, and thermal runaway reaction for CHP mixed with dry fire-extinguishing chemicals by vent sizing package 2. The results showed that ABC dry chemical, BC dry chemical, and XBC dry chemical all caused the decomposition of MEKPO to occur at lower onset temperature and H₂O caused the ΔH _d of MEKPO to become higher. On the other hand, H₂O and XBC dry chemical induced the decomposition of CHP to occur at lower onset temperature as well as lower thermal explosion temperature. The maximum of self-heating rate ((dT/dt)_max) and the maximum pressure-rise rate ((dP/dt)_max) of CHP mixed with dry fire-extinguishing chemicals were measured lower than CHP alone. The results indicated that MEKPO and CHP are highly hazardous when mixed with H₂O and some dry fire-extinguishing chemicals. In view of loss prevention, the results can be useful references for fire fighters dealing with thermal upsets in chemical plants.     

Effects of cumene hydroperoxide on phenol and acetone manufacturing by DSC and VSP2

Cumene hydroperoxide (CHP) being catalyzed by acid is one of the crucial processes for producing phenol and acetone globally. However, it is thermally unstable to the runaway reaction readily. In this study, various concentrations of phenol and acetone were added into CHP for determination of thermal hazards. Differential scanning calorimetry (DSC) tests were used to obtain the parameters of exothermic behaviors under dynamic screening. The parameters included exothermic onset temperature (T ₀), heat of decomposition (ΔH _d), and exothermic peak temperature (T _p). Vent sizing package 2 (VSP2) was employed to receive the maximum pressure (P _max), the maximum temperature (T _max), the self-heating rate (dT/dt), maximum pressure rise rate ((dP/dt)_max), and adiabatic time to maximum rate ((TMR)_ad) under the worst case. Finally, a procedure for predicting thermal hazard data was developed. The results revealed that phenol and acetone sharply caused a exothermic reaction of CHP. As a result, phenol and acetone are important indicators that may cause a thermal hazard in the manufacturing process.     

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.     

Reaction hazard analysis for the thermal decomposition of cumene hydroperoxide in the presence of sodium hydroxide

Organic peroxides have caused many serious explosions and fires that were promoted by thermal instability, chemical pollutants, and even mechanical shock. Cumene hydroperoxide (CHP) has been employed in polymerization and for producing phenol and dicumyl peroxide (DCPO). Differential scanning calorimetry (DSC) has been used to assess the thermal hazards associated with CHP contacting sodium hydroxide (NaOH). Thermokinetic parameters, such as exothermic onset temperature (T ₀), peak temperature (T _max), and enthalpy (ΔH) were obtained. Experimental data were obtained using DSC and curve fitting using thermal safety software (TSS) was employed to obtain the kinetic parameters. Isothermal microcalorimetry (thermal activity monitor, TAM) was used to investigate the thermal hazards associated with storing of CHP and CHP mixed with NaOH under isothermal conditions. TAM showed that in the temperature range from 70 to 90°C an autocatalytic reaction occurs. This was apparent in the thermal curves. Depending on the operating conditions, NaOH may be one of the chemicals or catalysts incompatible with CHP. When CHP was mixed with NaOH, the T ₀ is lower and reactions become more complex than those associated with assessment of the decomposition of the pure peroxide. The data by curve fitting indicated that the activation energy (E _a) for the induced decomposition is smaller than that for decomposition of CHP in the absence of hydroxide.     

Kinetics of catalyst-free thermal and photo-oxidation of cumene

Kinetics of thermal and photo-oxidation of cumene in the absence of catalyst was studied using high-pressure differential scanning calorimetry and low-pressure photocalorimetry. Kinetics of oxidation was followed by cumene hydroperoxide (CHP), acetophenone, and phenol formation. The amount of CHP formed was deduced from the total heat of reaction of thermal degradation of CHP at 453 K and using a new gas chromatographic method. CHP solution in cumene oxidized at 453 K and 680 psi of oxygen reproducibly with the heat of reaction linearly dependent on peroxide concentration in cumene. It was confirmed that cumene thermal oxidation was slow at <453 K, but at ≥453 K could occur explosively. Autocatalysis by CHP during thermo-oxidation was confirmed. Apparent activation energy of the photo-oxidation of cumene was found to be E _a = 22.3 kJ mol^?1. The value corresponds to radical chain process of the cumene autoxidation. Under assumption of pseudo-first order reaction, the rate constant of CHP formation was found to change from k _CHP ≈ 0.76 s^?1 during the first 4 h of photo-oxidation to k _CHP ≈ 0.2 s^?1 at the later stages at 2.0 W cm^?2 of UV exposure dose. It was established that the initial presence of the CHP in cumene does not change the photo-oxidation kinetics, but shifts the kinetic curve to earlier time. Finite difference method was employed to numerically model kinetics of cumene oxidation. The result indicated higher than expected thermal and photo-stability of both, cumene and CHP.     

Thermokinetic parameters and thermal hazard evaluation for three organic peroxides by DSC and TAM III

The thermokinetic parameters were investigated for cumene hydroperoxide (CHP), di-tert-butyl peroxide (DTBP), and tert-butyl peroxybenzoate (TBPB) by non-isothermal kinetic model and isothermal kinetic model by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III), respectively. The objective was to investigate the activation energy (E _a) of CHP, DTBP, and TBPB applied non-isothermal well-known kinetic equation to evaluate the thermokinetic parameters by DSC. We employed TAM III to assess the thermokinetic parameters of three liquid organic peroxides, obtained thermal runaway data, and then used the Arrhenius plot to obtain the E _a of liquid organic peroxides at various isothermal temperatures. In contrast, the results of non-isothermal kinetic algorithm and isothermal kinetic algorithm were acquired from a highly accurate procedure for receiving information on thermal decomposition characteristics and reaction hazard.     

Thermal hazard evaluation of tert-butyl peroxide using non-isothermal and adiabatic calorimetric approaches

Tert-butyl peroxide (TBPO), is a typical organic peroxides (OPs),which is widely applied as initiator in poly-glycidyl methacrylate (PGMA) reaction, and is employed to provide a free-radical in frontal polymerization, and which has also caused many thermal runaway reactions and explosions worldwide. To find an unknown and insufficient hazard information for an energetic material, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to detect the fundamental thermokinetic parameters involving the exothermic onset temperature (T ₀), heat of decomposition (??H _d), temperature rise rate (dT · dt ^?1), time to maximum rate under adiabatic situation (TMR_ad), pressure rise rate (dP · dt ^?1), and maximum pressure (P _max), etc. The T ₀ was calculated to be 130?°C using DSC and VSP2. Activation energy (E _a) of TBPO was evaluated to be 136?kJ?mol^?1 by VSP2. In view of the loss prevention, calorimetric applications and model evaluation to integrate thermal hazard development are adequate means for inherently safer design.     

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.     

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.     

Reactivity in the solid-state between ZnWO<Subscript>4</Subscript> and some rare-earth metal molybdates RE<Subscript>2</Subscript>MoO<Subscript>6</Subscript> (<Emphasis Type="Italic">RE</Emphasis>=Y,Sm, Eu,Gd, Dy,Ho, Er and Lu)

Organic peroxides (OPs) have caused many momentous explosions and runaway reactions, resulting from thermal instability, chemical pollutants, and even mechanical shock. In Taiwan, dicumyl peroxide (DCPO), due to its unstable reactive nature, has caused two thermal explosions and runaway reaction incidents in the manufacturing process. To evaluate thermal hazards of DCPO in a batch reactor, we studied thermokinetic parameters, such as heat of decomposition (†H _d), exothermic onset temperature (T ₀), maximum temperature rise ((dT/dt)_max), maximum pressure rise ((dP/dt)_max), self-heating rate (dT/dt), etc., via differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2).     

Thermal runaway evaluation of α-methylstyrene and trans-β-methylstyrene with benzaldehyde

Styrene is an important chemical in the petrochemical industry. In recent years, there have been sporadic releases, runaway reactions, fires, and thermal explosion accidents incurred by styrene and its derivatives worldwide. The purpose of this study was to estimate the impact of styrene and its derivatives of α-methylstyrene (AMS) and trans-β-methylstyrene (TBMS) contacting with benzaldehyde. Experiments were carried out to evaluate the thermokinetic parameters estimated by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III). TAM III was used to determine the fundamental thermokinetics under various isothermal temperatures, 80, 90 and 100°C. This autocatalytic reaction was demonstrated in thermal curves. After styrene was contacted with benzaldehyde, the exothermic onset temperature (T ₀) and the total heat of reaction (Q _total) were altered by DSC tests. When benzaldehyde is mixed with AMS and TBMS, the reaction time will be shorter but the enthalpy reduced, as revealed by TAM III tests. As AMS and TBMS, respectively, were contacted with benzaldehyde, both exothermic phenomena were changed during the reaction excursion. According to the results of this research, an operator should dictate the oxygen concentration in order to avoid any potential hazards during handling and transportation.     

Preparation and thermal reliability of <Emphasis Type="Italic">N</Emphasis>-butyl stearate/methyl palmitate composite phase change material

In this study, a series of binary mixtures of N-butyl stearate (nBS) and methyl palmitate (MP) were used to produce a novel composite phase change material (CPCM) for potential application in the eastern China, and their thermal properties were investigated by differential scanning calorimetry (DSC). The results of DSC indicated that the mixture consisting of 10 mass% nBS and 90 mass% MP is optimum as the CPCM in terms of the phase change temperature ranges (T _f = 19.74–5.59 °C; T _m = 18.34–33.80 °C) and latent heats (ΔH _f = 176.8 J g^?1; ΔH _m = 189.3 J g^?1). On the other hand, the thermal reliability and chemical stability of the CPCM after 120, 180, 240, 300, 360 and 500 accelerated thermal cycling tests were studied by DSC and fourier transform infrared (FTIR) analysis. The results demonstrated that the CPCM had good thermal reliability and chemical stability.     

Reaction hazard analysis for cumene hydroperoxide with sodium hydroxide or sulfuric acid

Organic peroxides (OPs) are very susceptible to thermal sources, chemical pollutants or even mechanical shock. Over the years, they have caused many serious explosions. Cumene hydroperoxide (CHP) is widely employed to produce phenol and dicumyl peroxide (DCPO) in the manufacturing process. Differential scanning calorimetry (DSC) and thermal activity monitor (TAM) were employed to determine the potential thermal hazards and thermokinetic parameters (such as exothermic onset temperature (T ₀), maximum temperature (T _max), and enthalpy (ΔH)) of CHP mixed with sodium hydroxide (NaOH) and sulfuric acid (H₂SO₄). High performance liquid chromatography (HPLC) was used to analyze the concentration vs. time of CHP.When CHP is mixed with NaOH, the T ₀ is induced earlier and reactions become more intricate than the pure CHP solution. CHP added to NaOH or H₂SO₄ is more dangerous than pure CHP alone. Depending on the operating conditions, NaOH and H₂SO₄ are the incompatible chemicals for CHP.     

Kinetics and thermodynamics of thermal decomposition of synthetic AlPO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O

Cumene hydroperoxide (CHP) and its derivatives have caused many serious explosions and fires in Taiwan as a consequence of thermal instability, chemical contamination, and even mechanical shock. It has been employed in polymerization for producing phenol and dicumyl peroxide (DCPO). Differential scanning calorimetry (DSC) was used to analyze the thermal hazard of CHP in the presence of sodium hydroxide (NaOH), sulfuric acid (H₂SO₄), and sodium bisulfite (Na₂SO₃). Thermokinetic parameters for decomposition, such as exothermic onset temperature (T ₀ ), maximum temperature (T _max ), and enthalpy (ΔH), were obtained from the thermal curves. Isothermal microcalorimetry (thermal activity monitor, TAM) was employed to investigate the thermal hazards during CHP storage and CHP mixed with NaOH, H₂SO₄, and Na₂SO₃ under isothermal conditions in a reactor or container. Tests by TAM indicated that from 70 to 90 °C an autocatalytic reaction was apparent in the thermal curves. According to the results from the TAM test, high performance liquid chromatography (HPLC) was, in turn, adopted to analyze the result of concentration versus time. By the Arrhenius equation, the activation energy (E _a ) and rate constant (k) were calculated. Depending on the process conditions, NaOH was one of the incompatible chemicals or catalysts for CHP. When CHP is mixed with NaOH, the T ₀ is induced earlier and the reactions become more complex than for pure CHP, and the E _a is lower than for pure CHP.     

Thermal explosion and runaway reaction simulation of lauroyl peroxide by DSC tests

Lauroyl peroxide (LPO) is a typical organic peroxide that has caused many thermal runaway reactions and explosions. Differential scanning calorimetry (DSC) was employed to determine the fundamental thermokinetic parameters that involved exothermic onset temperature (T₀), heat of decomposition (ΔH_d), and other safety parameters for loss prevention of runaway reactions and thermal explosions. Frequency factor (A) and activation energy (E_a) were calculated by Kissinger model, Ozawa equation, and thermal safety software (TSS) series via DSC experimental data. Liquid thermal explosion (LTE) by TSS was employed to simulate the thermal explosion development for various types of storage tank. In view of loss prevention, calorimetric application and model analysis to integrate thermal hazard development were necessary and useful for inherently safer design.     

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 parameters study of 1,1-bis(tert-butylperoxy)cyclohexane at low heating rates with differential scanning calorimetry

Having two active peroxide groups, 1,1-bis(tert-butylperoxy)cyclohexane (BTBPC) has a certain degree of thermal instability. It is usually used as an initiator in a chemical process, and therefore, careless operation could result in severe accidents. This study emphasized the runaway reactions of BTBPC 70 mass% (4.5–5.2 mg), the relevant thermokinetic parameters, and the thermal safety parameters. Differential scanning calorimetry was used to evaluate the above-mentioned thermokinetic parameters, using four low heating rates (0.5, 1, 2, and 4 °C min^?1) combined with kinetic simulation method. The results indicated that apparent exothermic onset temperature (T _o), apparent activation energy (E _a), and heat of decomposition (ΔH _d) were ca. 118 °C, 156 kJ mol^?1, and 1,080 kJ kg^?1, respectively. In view of process loss prevention, at the low heating rates of 0.5, 1, 2, and 4 °C min^?1, storing BTBPC 70 mass% below 27.27 °C is a more reassuring approach.