Authors:Sheng-Hung Wu, Meng-Lung Lin, and Chi-Min Shu
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 (T0), heat of decomposition (ΔHd), temperature rise rate (dT · dt−1), time to maximum rate under adiabatic situation (TMRad), pressure rise rate (dP · dt−1), and maximum pressure (Pmax), etc. The T0 was calculated to be 130 °C using DSC and VSP2. Activation energy (Ea) 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.
Authors:Shang-Hao Liu, Chun-Ping Lin, and Chi-Min Shu
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 (Ea) 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 Ea 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.
Authors:Sun-Ju Shen, Sheng-Hung Wu, Jen-Hao Chi, Yih-Wen Wang, and Chi-Min Shu
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
(ΔHd) and exothermic onset temperature (T0), 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, T0, heat of decomposition (ΔHd), and activation energy (Ea) of DCPO mixed with HNO3 were calculated to be 70 °C, 911 J g−1, and 33 kJ mol−1, respectively.
Authors:Mei-Li You, Ming-Yang Liu, Sheng-Hung Wu, Jen-Hao Chi, and Chi-Min Shu
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 (ΔHd), and other safety parameters for loss prevention of runaway reactions and thermal explosions. Frequency factor (A) and activation
energy (Ea) 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.
Authors:Jiann-Rong Chen, Shyh-Yuch Cheng, Min-Hao Yuan, Arcady Kossoy, and Chi-Min Shu
A hierarchical set of kinetic models were proposed and discussed for simulation of autocatalytic decomposition of cumene hydroperoxide
(CHP) in cumene at low temperatures. The hierarchy leads from a formal model of full autocatalysis, which is based on conversion
degree as a state variable, through a two-stage autocatalytic concentration-based model to a meticulous multi-stage model
of the reaction. By the ForK (Formal Kinetics) and DesK (Descriptive Kinetics) software, developed by ChemInform Saint Petersburg
(CISP) Ltd., the related kinetic parameters and their significance have also been estimated and elucidated. Through this best-fit
approach, it is possible to formulate a systematic methodology on the kinetic studies for thermal decomposition of typical
organic peroxides with autocatalytic nature, specifically at low temperature ranges.
Authors:Hung-Cheng Chou, Sheng-Hung Wu, Chung-Cheng Chiang, Jao-Jia Horng, Jen-Hao Chi, and Chi-Min Shu
Oxygen (O2) or air is widely applied globally to yield cumene hydroperoxide (CHP) in a cumene oxidation tower. In previous studies, CHP has been identified as a thermally hazardous chemical. This study was used to evaluate thermal hazard of CHP in cumene using differential scanning calorimetry and vent sizing package 2 (VSP2). Self-accelerating decomposition temperature (SADT), self-heating rate, exothermic onset temperature (T0), critical temperature (Tc), time to maximum rate (TMR), activation energy (Ea), etc., were employed to prevent and protect thermal runaway reaction and explosion in the manufacturing process and/or storage area. The reaction order (n) of CHP was evaluated to be 0.5 in this study. The Ea was determined to be 122 kJ mol−1 by VSP2. High volume of CHP with 0 rpm of stirring rate by VSP2 was more dangerous than a low one. Control of stirring rate should be a concern in process safety management program. In view of proactive loss prevention, inherently safer handling procedures and storage situations should be maintained in the chemical industries.
Authors:Sheng-Hung Wu, Jen-Hao Chi, Chun-Chin Huang, Nung-Kai Lin, Jiou-Jhu Peng, and Chi-Min Shu
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.
Authors:Mei-Li You, Jo-Ming Tseng, Ming-Yang Liu, and Chi-Min Shu
Pooling lauroyl peroxide (LPO) with nitric acid, we used differential scanning calorimetry (DSC) to assess the thermokinetic
parameters, such as exothermic onset temperature (T0), heat of decomposition (ΔHd), frequency factor (A), and the other safety parameters. When LPO was contaminated with nitric acid (HNO3), we found the exploder 1-nitrododecane. Obvious products were sensitive and hazardous chemicals. Concentration reaching
1–12 N HNO3 emitted a large amount of heat. This study combined with curve-fitting method to elucidate its unsafe characteristics and
thermally sensitive structure to help prevent runaway reactions, fires and explosions in the process environment. According
to the findings and the concept of inherently safer design, LPO runaway reactions could be adequately prevented in the relevant
Authors:Yu-Chuan Chou, Tung-Feng Hsieh, Yu-Chen Hsieh, Chun-Ping Lin, and Chi-Min Shu
Multi-walled carbon nanotubes (MWCNTs) have remarkable properties. However, their thermal stability characteristics, which
may represent potential hazards during the production or utilization stage, concern unsafe or unknown properties researches.
Our aim was to analyze the thermokinetic parameters of different heating rates by differential scanning calorimetry (DSC)
and thermogravimetric analyzer (TG), and then to compare thermal decomposition energy parameters under various conditions
by well-known kinetic equations. MWCNTs were acidified via nitric acid (HNO3) in various concentrations from 3 to 15 N and were characterized by means of Fourier transform infrared (FTIR) spectrometry.
For original and modified MWCNTs, we further identified the thermal degradation characteristics of the functional group by
TG-FTIR. Finally, we established an effective and prompt procedure for receiving information on thermal decomposition characteristics
and reaction hazard of MWCNTs that could be applied as an inherently safer design during normal or upset operation.
Authors:Chun-Ping Lin, Yi-Ming Chang, Jo-Ming Tseng, and Chi-Min Shu
Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a typical highly energetic material that has been widely used in
national defense industries since the 1940s. The aim of this study was to establish a reaction kinetic model on thermal decomposition
properties via differential scanning calorimetry (DSC) by well-known kinetic equations and kinetic model simulation. Furthermore,
the aim also was to compare kinetic algorithms for thermal decomposition energy parameters under various conditions. Experimental
results highly depended on the reliability of the kinetic concept applied, which is essentially defined by the proper choice
of a mathematical model of a reaction. In addition, the correctness of the methods is used for kinetics evaluation.