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Polymerization is a typical exothermic reaction in the fine chemical industry, which is easy to cause thermal runaway. In order to lower the thermal runaway risk of polymerization, a microreactor was adopted in this study to carry out styrene thermal polymerization. The hydrodynamic model and the fluid–solid coupling model of thermal polymerization of styrene were combined by using the computation fluid dynamics (CFD) method to build a three-dimensional steady-state model of the batch and the microreactor and compare. The results indicated that the maximum temperature of the polymerization in the microreactor was only 150.23 °C, while in the batch reactor, it was up to 371.1 °C. Therefore, the reaction temperature in the microreactor could be controlled more effectively compared with that in the batch reactor. During the reaction process, jacket cooling may fail, which would lead to an adiabatic situation. According to the divergence criterion (DIV), the thermal runaway of the polymerization occurred in microreactors with different tube diameters under an adiabatic situation. Further, the diameter of the microreactor had a considerable effect on the distribution of the inside temperature field under normal jacket cooling. The maximum temperature difference in the microreactor with a diameter of 6 mm was controlled at 25.33 °C. However, the effects of the inlet velocity (0.001, 0.0015, 0.002, 0.0025, 0.003 m/s), jacket temperature (150, 170, 180, 190, 200 °C) and residence time (400, 500, 600, 750 s) were relatively small. In addition, the jacket temperature had significant effects on viscosity, while other conditions had little effect. The DIV criterion indicated that the styrene thermal polymerization reactions could be safely performed in the microreactor when the jacket was cooled normally.

Thermal Hazard Analysis of Styrene Polymerization in Microreactor of Varying Diameter