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JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES · 2024 · IF 3.6

Temperature control for the synthesis of n-butylmagnesium bromide Grignard reagent based on n-octadecane/polystyrene microPCMs

Dongyan Yang,Lei Ni,Luping Gu,Qiang Chen,Juncheng Jiang,Jimi Su

Thermal runaway accounts for a high proportion of chemical safety accidents and poses a serious threat to the operational safety of personnel. Phase change materials (PCMs) have a high enthalpy of melting, if the latent heat energy of their phase change can be stored and used to absorb the heat released during thermal runaway, this phenomenon can provide a new approach for the control of reaction thermal runaway. In this work, microencapsulated phase change materials (microPCMs) were prepared by the suspension polymerization method using n -octadecane as the core material and polystyrene (PS) as the shell material. The prepared microPCMs had regular spherical morphologies with smooth surfaces, and the average particle size was 7.54 μm, the thermal conductivity was 0.05964 W/m∙K. The melting enthalpy of the microPCMs was 142.2 J/g, and the encapsulation percentage of the PCMs was 62.15%. The synthesis of the n -butylmagnesium bromide Grignard reagent occurred via a strong exothermic reaction, which was very likely to lead to overpressure venting once control was lost. The prepared microPCMs were applied as inhibitors in this reaction to investigate the temperature control effect under different operating conditions. The results showed that the amount of microPCMs added, and the timing of the addition affected the control effect. The addition of microPCMs could effectively reduce the reaction temperature and slow the rate of temperature increase. Even in the event of an emergency situation, such as a control failure, time could be gained for other emergency measures, effectively reducing the probability of thermal runaway accidents.

CAS / MDL: 94-36-0 593-45-3
研究领域: 化学工程 · 材料科学
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THERMOCHIMICA ACTA · 2022 · IF 3.378

Thermal hazard assessment of cyclohexane-type liquid crystal monomer from the Grignard cross-coupling reaction by different calorimeters

Wei Wang,Jiancun Gao,Yujing Li,Shengnan Wang,Chenguang Shi,Xiong Dai,Tianmeng Jiang,Guangming Sun

The thermal hazard assessment of cyclohexane-type liquid crystal monomers (CLCMs) from the Grignard cross-coupling reaction is challenging because the thermal hazard assessment involves the Grignard reagent. In this study, different calorimeters in semi-batch and batch modes were used to investigate the exothermic behaviour of CLCM. The enthalpy of formation of the Grignard reagent (320.87 - 380.46 kJ mol −1 ) was higher than that of the cross-coupling reaction (70.92 - 108.68 kJ mol −1 ). The heat accumulation in semi-batch mode decreased to 12.15% when compared with 100% observed in batch mode. Furthermore, the Grignard reagent decomposed at 470.39 K, with a low activation energy ( E a ) of 110.99 - 129.67 kJ mol −1 . Finally, based on the Stoessel criticality diagram, the thermal risk of the CLCM was found to be class 4 in batch mode and class 3 in semi-batch mode. This revealed that the semi-batch mode was the most suitable dosing method for CLCMs.

研究领域: 化学工程 · 材料科学
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