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Epoxidized soybean oil (ESO) is a sustainable alternative that reduces emissions of volatile organic compounds, enhances coating and adhesion properties, and has a wide range of applications in bio-based composites. However, the industrial-scale production of ESO through the Prilezhaev reaction presents challenges in terms of temperature regulation and the potential for uncontrolled thermal reactions. This study aimed to investigate the thermal hazards associated with ESO production using hydrogen peroxide. We analyzed the reaction mechanism and exothermic behavior using dynamic differential scanning calorimetry (DSC), accelerated calorimetry (ARC), reaction calorimetry (RClmx), and in situ Fourier transform infrared spectroscopy (FTIR). Our findings demonstrated that the addition of sulfuric acid and formic acid raised the onset decomposition temperature of hydrogen peroxide. We also identified two exothermic phases (epoxidation of the double bond and degradation of the organic matter) and observed a rapid increase in temperature and pressure, posing a safety risk. Formic acid formation and epoxidation of the double bond were the main steps of the reaction mechanism, and the exothermic behavior stems mainly from the latter. We assessed the thermal hazard level using a risk matrix and the Stoessel criterion, which highlighted the high risk of thermal runaway without proper cooling and temperature control. This paper offers practical guidance for mitigating these risks in the industry. [ABSTRACT FROM AUTHOR]

The epoxidation process of soybean oil (SBO) and peracid produced by 50 wt% hydrogen peroxide (H2O2) and formic acid (FA) was studied with sulfuric acid (H2SO4) as a catalyst. Three reaction parameters, including reaction temperature, FA-to-SBO ratio, and H2O2-to-SBO ratio, were investigated, along with the combined effect on oxirane value (OV). Based on response surface methodology (RSM), the Box-Behnken design (BBD) was used to optimize the process parameters. According to the results, the calculated OV (7.34%) and the experimental OV (7.31%) were signifi cantly in agreement. The product was confi rmed as epoxidized soybean oil (ESO) by IR and NMR characterization methods. These results demonstrated the reliability of RSM to optimize the SBO reaction to produce ESO with high oxygen content. [ABSTRACT FROM AUTHOR]

• [(C 18 H 37) 2 (CH 3)2N] 3 {PO 4 [W(O)(O 2) 2 ] 4 } improves hydrogen peroxide stability. • The reaction exhibits autocatalytic properties. • The established mathematical model accurately calculates the reaction enthalpy. • High risk of thermal runaway in this reaction. This paper explores an efficient and eco-friendly epoxidation process using the phase transfer catalyst ([(C 18 H 37) 2 (CH 3) 2 N] 3 {PO 4 [W(O)(O 2) 2 ] 4 }), which offers more advantages over the use of carboxylic and inorganic acids as catalysts in the Prileschajew epoxidation process. Consequently, a study of the process's thermal hazards is imperative. The paper conducts a comprehensive analysis of the process, employing a combination of calorimetric techniques. The critical runaway temperature, stabilization temperature, and required heat dissipation rate to prevent thermal runaway reactions were calculated using the Semenov model. On-line Fourier transform infrared spectroscopy and reaction calorimetry were used to relate the reaction mechanism and exothermic behavior of the actual production process, and a reliable model was developed for the calculation of reaction enthalpy. The findings indicate that the thermal risk depends on the rate of double bond epoxidation, which provides offering valuable insights for safe industrial-scale ESO production. [Display omitted] [ABSTRACT FROM AUTHOR]

• A novel amphiphilic phase transfer catalyst [(C 18 H 37) 2 (CH 3) 2 N] 3 {PO 4 [W(O)(O 2) 2 ] 4 } was developed. • The developed catalysts showed excellent catalytic performance for the epoxidation of soybean oil. • The developed catalyst was easily separable and maintained its activity after five cycles. • The catalytic mechanism was explored using FT-IR spectroscopy. • The interfacial properties of the developed catalyst were studied. Epoxidized soybean oil (ESO) is a vital organic renewable chemical material widely used in the preparation of biomaterials. In this paper, a novel amphiphilic phase transfer catalyst [(C 18 H 37) 2 (CH 3) 2 N] 3 {PO 4 [W(O)(O 2) 2 ] 4 } was developed to facilitate the green, safe and sustainable production of ESO, with the aim of achieving maximum environmental and economic benefits. Soybean oil (SBO) was epoxidized into ESO at a conversion rate of 98.6% and the selectivity of this process was above 99% with H 2 O 2 as the oxidant. The catalyst was easily separable through filtration after the reaction, and its activity was found to be consistently maintained after 5 cycles. The developed catalysts were characterized via various physical means such as Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM), while the catalytic mechanism was explored using FT-IR spectroscopy. Several kinetic and thermodynamic experiments suggested that the developed catalyst possessed significant interfacial activity and the process followed a non-spontaneous endothermic pathway. [Display omitted] [ABSTRACT FROM AUTHOR]