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首页> 外文期刊>Organic process research & development >Predicting 24 and 8 h Adiabatic Decomposition Temperature for Low Temperature Reactions by Kinetic Fitting of Nonisothermal Heat Data from Reaction Calorimeter (RC1e)
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Predicting 24 and 8 h Adiabatic Decomposition Temperature for Low Temperature Reactions by Kinetic Fitting of Nonisothermal Heat Data from Reaction Calorimeter (RC1e)

机译：通过反应量热仪（RC1e）的非等温热数据的动力学拟合预测低温反应的24和8 h绝热分解温度

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摘要

A new approach to determine the adiabatic decomposition temperature in 24 or 8 h (ADT 24/ADT 8) using a combination of nonisothermal heat data and kinetic modeling for the low temperature decomposition of a lithiated halogenated aromatic intermediate via the formation of a highly unstable benzyne intermediate is presented here. First order rate equations for the two steps were used for fitting the experimental heat curve generated from the temperature ramp of the lithiated reaction mass in RCIe. A good fit of experimental and predicted heat generation curves was obtained by fitting the kinetic parameters in DynoChem software using the heat data generated from the non-isothermal run in RC1e. The decomposition of a lithiated intermediate to a benzyne intermediate is a slow reaction and is sensitive to temperature, with rate constant (k) and activation energy (E_a) of 4.08 X 10~(-8) 1/s (reference temperature T_(ref) = -67 °C) and 99 kJ/mol, respectively. The decomposition of benzyne is a fast reaction and insensitive to temperature, with rate constant (k) and activation energy (E_a) of 1.34 X 10~(-3) 1/s (T_(ref) = -67 °C) and 2.3 kj/mol, respectively. The kinetic parameters obtained from the fitting were then used to predict the ADT 24/ADT 8 and determine the maximum safe operating temperature for scale up. Kinetic studies indicate that dilution of the reaction with additional solvent has a minor impact on the predicted ADT 24 and ADT 8 and the decomposition is a strong function of temperature. Through this case-study, the methodology of using the heat curve from a single temperature ramp experiment in RCIe for fitting the low temperature decomposition kinetics and evaluating the criticality of the process step is demonstrated.
机译：结合非等温热数据和动力学模型，通过形成高度不稳定的苯甲醛，低温分解锂化卤代芳族中间体的新方法，以确定24或8 h的绝热分解温度（ADT 24 / ADT 8）中间体在这里介绍。这两个步骤的一阶速率方程式用于拟合从RCIe中锂化反应物料的温度斜线生成的实验热曲线。通过使用在RC1e中非等温运行产生的热量数据拟合DynoChem软件中的动力学参数，可以很好地拟合实验和预测的发热曲线。锂化中间体分解为苯并中间体是一个缓慢的反应并且对温度敏感，速率常数（k）和活化能（E_a）为4.08 X 10〜（-8）1 / s（参考温度T_（ref ）= -67°C）和99 kJ / mol。苯并炔的分解是快速反应且对温度不敏感，速率常数（k）和活化能（E_a）为1.34 X 10〜（-3）1 / s（T_（ref）= -67°C）和2.3 kj / mol。然后，将从拟合中获得的动力学参数用于预测ADT 24 / ADT 8并确定按比例放大的最大安全工作温度。动力学研究表明，用其他溶剂稀释反应对预测的ADT 24和ADT 8的影响较小，分解是温度的强函数。通过此案例研究，展示了使用RCIe中单个温度斜坡实验的热曲线来拟合低温分解动力学并评估工艺步骤的关键性的方法。

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