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  • Author or Editor: Shu Liu x
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Abstract  

Pooling lauroyl peroxide (LPO) with nitric acid, we used differential scanning calorimetry (DSC) to assess the thermokinetic parameters, such as exothermic onset temperature (T 0), heat of decomposition (ΔH d), 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 plants.

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Abstract  

In this study, α-phase nucleating agent (NA) 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (DMDBS), β-phase rare earth NA (WBG), and their compound NAs were introduced into isotactic polypropylene (iPP) matrix, respectively. Crystallization kinetics and subsequent melting behavior of the nucleated iPPs were comparatively studied by differential scanning calorimetry (DSC) under both isothermal and nonisothermal conditions. For the isothermal crystallization process, it is found that the Avrami model successfully described the crystallization kinetics. The active energy of nonisothermal crystallization of iPP was determined by the Kissinger method and showed that the addition of nucleating agents increased the activation energy. Melting behavior and crystalline structure of the nucleated iPPs are dependent on the nature of NAs and crystallization conditions. Higher proportion of β-phase can be obtained at higher content of β-nucleating agent and lower crystallization temperature or lower cooling rate.

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Abstract  

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.

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Abstract  

SBA-15 materials were synthesized through the hydrothermal method. The SBA-15 prepared at the hydrothermal time of 24 h possessed a higher surface area and a good hexagonal structure, so it was used as the catalytic support in this experiment. The base metals (Cu, Co, Ni) coated on SBA-15 were prepared for toluene removal. The results revealed that the catalytic activity of Cu/SBA-15 for toluene removal was about 70% at 250 °C, which was the best among the three catalysts. The modification of Cu/SBA-15 by adding different transition metals (Ce, Co, Ni, Mn) to improve the removal efficiency of toluene and NO was also investigated in this study. The results indicate that the catalytic activity of Mn–Cu/SBA-15 for toluene removal was about 100% at 250 °C. The toluene as a reductant on the removal of NO was also determined. Furthermore, the catalytic activity of Mn–Cu/SBA-15 for NO removal can reach about 70% at 300 °C when toluene is used as reductant.

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Abstract  

Gd2O3/Ag3VO4 photocatalysts are synthesized through the impregnation method and characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectra (DRS). It is shown that Gd3+ is dispersed on the surface of Ag3VO4 in the form of Gd2O3. The DRS analysis indicates that the ability of visible-light absorption of Gd2O3/Ag3VO4 catalysts is enhanced greatly. The photocatalytic activities of the samples are evaluated by degradation of Rhodamine B dye under UV and visible-light irradiation, respectively. The experimental results show that the role of Gd2O3 content has a significant impact on the photocatalytic activities of the samples. The mechanism of enhanced photocatalytic activity after the Gd introduction is discussed.

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Four geminal ionic liquids (GILs), namely, 1,4-bis(1,1′-butyl-3,3′- methylene- imidazolium)-benzene bis[(trifluoromethyl)sulfonyl]imide (BBMIB-NTf2), 1,4- bis(1,1′-butyl-3,3′-methylene-imidazolium)-benzene tetrafluoroborate (BBMIB-BF4), 1,4- bis(1,1′-butyl-3,3′-methylene-imidazolium)-benzene hexafluophosphate (BBMIB-PF6), and 1,4-bis(1,1′-methyl-3,3′-methylene-imidazolium)-benzene bis[(trifluoromethyl) sulfonyl] imide (BMMIB-NTf2), were synthesized. They were statically coated onto the inner walls of fused-silica capillary columns and used as stationary phases for gas chromatography. The evaluation of BBMIB-NTf2, BBMIB-BF4, BBMIB-PF6, and BMMIB-NTf2 as stationary phases is reported here for the first time. These new stationary phases exhibit efficiencies of at least 2.3 × 103 plates per meter. Abraham solvation parameter model was used to evaluate the solvation characteristics. The system constants indicated that the dipolarity/polarizability and the hydrogen-bond basicity play a major role among five molecular interactions between stationary phases and solute molecules. A fundamental understanding into the solvation characteristics of these GILs can be used as a guide to choosing the appropriate geminal ionic liquids for specific applications in various fields. The chromatographic separation performance was evaluated by a Grob test mixture, n-alkanes, alcohols, and aromatic isomers. Furthermore, the thermal stability was tested. The present results demonstrate that these geminal ionic liquids stationary phases possess excellent chromatographic separation performance and good thermal stability (at least up to 270 °C) and may be applicable as gas chromatography stationary phases for more application.

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Abstract

The decomposition of organic peroxides by their relatively weak oxygen linkage and hydroperoxide radical in the presence of reaction solution is one of the thermal hazards for triggering a runaway reaction. Runaway incidents may occur in oxidation reactors, vacuum condensation reactors, tank lorries, or storage tanks. In NFPA 432 organic peroxides in NFPA 432 are classified as flammable. The exothermic behaviors of solid organic peroxides, dicumene peroxide, benzoyl peroxide, and lauroyl peroxide, were determined by differential scanning calorimetry (DSC), and vent sizing package 2 (VSP2). Relevant data detected by DSC provided thermal stability information, such as exothermic onset temperature (T 0), maximum heat-releasing peak (T max), and heat of decomposition (ΔH d). VSP2 was used to perform the bench scale situation for pushing the expected or unexpected reaction to undergo runaway reaction. Onset temperature, maximum pressure, self-heating rate ((dT dt −1)max), and pressure-release rate ((dP dt −1)max) were therefore obtained and explained. These results are essentially crucial in process design for an inherently safer approach.

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Journal of Thermal Analysis and Calorimetry
Authors: Chun-Ping Lin, Jo-Ming Tseng, Yi-Ming Chang, Shang-Hao Liu, Yen-Chun Cheng, and Chi-Min Shu

Abstract  

This study investigated the role played by green thermal analysis technology in promoting the use of resources, preventing pollution, reducing energy consumption and protecting the environment. The chemical tert-butyl peroxybenzoate (TBPB) has been widely employed in the petrifaction industries as an initiator of polymerization formation agent. This study established the thermokinetic parameters and thermal explosion hazard for a reactor containing TBPB via differential scanning calorimetry (DSC). To simulate thermokinetic parameters, a 5-ton barrel reactor of liquid thermal explosion model was created in this study. The approach was to develop a precise and effective procedure on thermal decomposition, runaway, and thermal hazard properties, such as activation energy (E a), control temperature (CT), critical temperature (TCR), emergency temperature (ET), heat of decomposition (∆H d), self-accelerating decomposition temperature (SADT), time to conversion limit (TCL), total energy release (TER), time to maximum rate under isothermal condition (TMR iso), etc. for a reactor containing TBPB. Experimental results established the features of thermal decomposition and huge size explosion hazard of TBPB that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.

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Abstract  

Methyl ethyl ketone peroxide (MEKPO) is an unstable material above certain limits of temperature, decomposing into chain reactions by radicals. The influence of runaway reactions on this basic characteristic was assessed by evaluating kinetic parameters, such as activation energy (E a), frequency factor (A), etc., by thermal activity monitor III (TAM III). This was done under three isothermal conditions of 70, 80, and 90 °C, with MEKPO 31 mass% combined with nitric acid (HNO3 6 N) and sodium nitrate (NaNO3 6 N). Nitric acid mixed with MEKPO gave the maximum heat of reaction (△H d) and also induced serious reactions in the initial stage of exothermic process under the three isothermal temperatures. The time to maximum rate (TMR) also decreased when HNO3 was mixed with MEKPO. Thus, MEKPO combined with HNO3 6 N forms a very hazardous mixture. Results of this study will be provided to relevant plants for alerting their staff on adopting best practices in emergency response or accident control.

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Abstract

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 (ΔH d), activation energy (E a), self-accelerating decomposition temperature, and isothermal time to maximum rate (TMRiso). 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.

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