Thermal hazard assessments in process industries often require calorimetry and kinetic modeling. These techniques are illustrated using examples of inhibited 4-vinylbenzyl chloride (VBC) self-polymerization and di-4-methylbenzoyl peroxide (MeBPO) thermal stability. The polymerization kinetics of inhibited VBC were studied using isothermal and non-isothermal calorimetry. A thermokinetic model was developed using calorimetry data and this model was coupled with a heat balance to predict the consequence of a commonly encountered plant scenario, loss of active cooling to a storage tank. Isothermal differential scanning calorimetry (DSC) and microcalorimetry (using a TAM IV microcalorimeter) were also applied to analyze the thermal decomposition of MeBPO desensitized with silicone oil (50% w/w). The thermokinetic parameters and thermal stability were evaluated. MeBPO decomposes in two exothermic reactions, and the total heat of decomposition was determined to be 658.8 J/g of sample. The thermal decomposition of MeBPO was described by a model of two parallel reactions, the first leading to 4,4′-dimethylbiphenyl and the second to p-methylbenzyl p-toluate. The results can be applied for emergency relief system design and for emergency rescue strategies during an upset or accident.

中文翻译：

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DSC 和 TAM 对 4-乙烯基苄基氯化物储存和二-4-甲基过氧化苯甲酰热分解的动力学和危害

过程工业中的热危害评估通常需要量热法和动力学模型。这些技术使用抑制 4-乙烯基苄基氯 (VBC) 自聚合和二 4-甲基过氧化苯甲酰 (MeBPO) 热稳定性的示例进行说明。使用等温和非等温量热法研究了受抑制的 VBC 的聚合动力学。使用量热法数据开发了一个热动力学模型，该模型与热平衡相结合，以预测常见工厂场景的后果，即主动冷却至储罐的损失。等温差示扫描量热法 (DSC) 和微量热法（使用 TAM IV 微量热仪）也用于分析用硅油（50% w/w）脱敏的 MeBPO 的热分解。评估了热动力学参数和热稳定性。MeBPO 在两个放热反应中分解，总分解热测定为 658.8 J/g 样品。MeBPO 的热分解由两个平行反应模型描述，第一个反应生成 4,4'-二甲基联苯，第二个反应生成对甲基苄基对甲苯甲酸酯。结果可用于紧急救援系统设计和突发事件或事故期间的紧急救援策略。