Mixing hazard evaluation of organic peroxides with other chemicals

Nine of commercially available organic peroxides were assessed with differential scanning calorimeter (DSC) and adiabatic calorimeters. These organic peroxides are cumene hydroperoxide (CHP), di-tert-butyl peroxide (DTBP), methyl-ethyl-ketone peroxide (MEKPO), tert-butyl hydroperoxide (TBHP), benzoyl peroxide (BPO), hydrogen peroxide, lauroyl peroxide (LPO), tertbutyl peroxybenzoate (TBPBZ), and dicumyl peroxide (DCPO). Exothermic onset temperatures, self-heat temperature and pressure rates, and heats of decomposition were measured and assessed. Adiabatic runaway reaction characteristics were determined by using ARC (accelerating rate calorimeter) and VSP2 (vent sizing package). Incompatibility, tests with several potential contaminants, was made using DSC, VSP2, and microcalorimeter. An incompatibility rating was developed using onset temperature, lowering of the onset temperature, heat of decomposition, maximum self-heat rate, adiabatic temperature rise, maximum pressure of decomposition, and maximum pressure rising rate, etc.

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“…Tables 2 and 3 summarize the decomposition results of organic peroxides from literature 15–19, 27–45.…”

Section: Resultsmentioning

confidence: 99%

Hazard ratings for organic peroxides

Duh

Kao

2008

Process Safety Progress

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“…Unexpected chemical reactions triggered by the mixing of chemicals may occur in chemical processes [1]. Such mixing may cause runaway reactions leading to the destruction of equipment [2].…”

Section: Introductionmentioning

confidence: 99%

Mixing hazard evaluation using small-scale Dewar vessels

Suzuki

Izato

Yoshino

et al. 2019

J Therm Anal Calorim

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In mixing hazard evaluations, a smaller scale is preferred for safety reasons and in order to conserve the samples. We have developed a small-scale Dewar vessel test (SDVT) that measures the amount of heat from a temperature change upon the mixing of two chemicals. In general, the accuracy of small-scale tests is negatively impacted by heat loss. The purpose of this study is to establish experimental conditions and to validate the reproducibility and accuracy of our small-scale test. The adjustable experimental parameters for SDVT are: position of sample injection, amount of sample, stirring speed, and surrounding temperature. These conditions were optimized for the measurement of the heat of neutralization of hydrochloric acid and sodium hydroxide. Under the optimized experimental conditions, the reproducibility was validated by measurement of the heat of hydration between acetic acid anhydride and water. The relative standard deviation of the maximum temperature change was 3.1%. To validate the accuracy, the heat of reaction between the neutralization reaction and hydration reaction was calculated. The heat of reaction was in good agreement with the theoretical value. Thus, the SDVT has sufficient accuracy and reproducibility to serve as a screening method for the mixing hazard of chemicals.

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“…On the other hand, alkyl hydroperoxides as the initial product of autoxidation often exist in the reaction mixture of industrial aerobic oxidation of hydrocarbons and also in the long-time-stored chemicals. However, due to their instability, alkyl hydroperoxides have caused many accidents so far, and they are designated as dangerous goods in regulations . Furthermore, for industrial aerobic oxidation, alkyl hydroperoxides always can hardly be the target products, and they will decompose and react further to become more stable valuable products, such as ketone, alcohol, acid, etc.…”

Section: Introductionmentioning

confidence: 99%

Selective Decomposition of Alkyl Hydroperoxides on H-Type Zeolite via a Concerted Approach

et al. 2009

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Catalyzed by H-type zeolite, the selective decomposition of alkyl hydroperoxides (HP), including 1-phenylethyl hydroperoxide (PEHP), phenylmethyl hydroperoxide (PMHP), and methyl hydroperoxide (MHP), to their corresponding carbonyl compounds and H2O have been investigated by DFT calculations. In this calculation, a 19-atom cluster containing four tetrahedral atoms (denoted as 4T) was used to model the H-type zeolite catalyst, and two competitive reaction channels were evaluated. Calculations predict that the concerted reaction channel is favorable for selective decomposition of alkyl hydroperoxides on the H-type zeolite from both kinetics and thermodynamics points of view. We found that the rate-determining step of the stepwise reaction channel proceeds via a one-hydrogen-bond transition state followed by dehydration. In the concerted reaction channel, whose transition state is an eight-membered ring with two hydrogen bonds, the decomposition of hydroperoxides occurs synchronously to form carbonyl compounds and H2O, involving the proton exchange between hydroperoxides and the zeolite.

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Mixing hazard evaluation of organic peroxides with other chemicals

Cited by 14 publications

References 2 publications

Hazard ratings for organic peroxides

Hazard ratings for organic peroxides

Mixing hazard evaluation using small-scale Dewar vessels

Selective Decomposition of Alkyl Hydroperoxides on H-Type Zeolite via a Concerted Approach

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